Novel substituted pyrazole derivative, process for producing the same, and herbicidal composition containing the same

ABSTRACT

Substituted pyrazole compounds of the formula (1). The compounds are synthesized from a pyrazole derivative and a haloalkyleneoxime ester derivative, and have excellent herbicidal effects. Herbicide compositions containing the substituted pyrazole derivatives or hydrazide derivatives thereof as active ingredients possess wide herbicidal spectra, work sufficiently in small dosages, and are sufficiently safe for certain important crops.

FIELD OF THE INVENTION

The present invention relates to novel substituted pyrazole derivatives,production process thereof, and herbicide compositions containing thederivative(s) as active ingredient(s). More particularly, the inventionrelates to substituted pyrazole derivatives useful as herbicides,production process thereof, and herbicide compositions containing thederivative(s) as active ingredient(s). These are advantageous in thechemical industry and agriculture, particularly in the field ofproduction of agricultural chemicals.

BACKGROUND OF THE INVENTION

Herbicides developed so far and used are numerous. However, there aremany species of weeds to be controlled, and emergence of the weeds lastsover a long period of time. Therefore, none of the many herbicideproducts can satisfy all the requirements in terms of, for example,herbicidal activity, herbicidal spectrum, crop selectivity, harmlessnessto humans and environmental loads.

In cultivation of particularly important crops such as wheat, corn,soybean and rice, a herbicide is desired that has effective herbicidalactivity even in a small dose, broad herbicidal spectrum, sufficientresidual effectiveness and excellent crop selectivity.

Attempts to search for pyrazoles having herbicidal activity forapplication in herbicides have been unsuccessful. The present applicanthas disclosed substituted pyrazole derivatives as fungicides andsynthesis processes thereof (Patent documents 1 to 3). However, thesedocuments do not provide any description as to herbicidal activity ofthe derivatives.

-   Patent document 1: JP-A-H10-130106-   Patent document 2: JP-A-H10-158107-   Patent document 3: EP 00 945 437 A1

DISCLOSURE OF THE INVENTION

The present inventors synthesized novel substituted pyrazole derivativesrepresented by the following formula (1) and made various studiesthereof. As a result, they have found that the derivatives haveexcellent herbicidal effects on a wide range of weeds includinguncontrollable weeds and show sufficient harmless to some importantcrops. Based on the findings, the present invention has beenaccomplished.

It is an object of the present invention to provide novel compounds thatare harmless to crops and have high herbicidal effects. The inventionhas an object of providing novel substituted pyrazole derivatives of thefollowing formula (1) (hereinafter “inventive compounds”) and herbicide.compositions containing the derivative(s) as active ingredient(s).

The summary of the present invention is as follows.

The inventive compound is a substituted pyrazole derivative representedby the formula (1):

wherein:

-   -   n is 0 or 1; independently    -   a group A is a hydrogen atom, a branched or unbranched alkyl        group of 1 to 4 carbon atoms, a branched or unbranched haloalkyl        group of 1 to 4 carbon atoms, a cycloalkyl group of 3 to 6        carbon atoms, or a phenyl group optionally having substituent        groups;    -   said substituent groups being the same as or different from one        another and selected from branched or unbranched alkyl groups of        1 to 4 carbon atoms, branched or unbranched haloalkyl groups of        1 to 4 carbon atoms, branched or unbranched alkoxy groups of 1        to 4 carbon atoms, hydroxyl group, branched or unbranched        haloalkoxy groups of 1 to 4 carbon atoms, branched or unbranched        alkylcarbonyloxy groups of 1 to 4 carbon atoms,        cycloalkylcarbonyloxy groups of 3 to 6 carbon atoms, branched or        unbranched alkoxycarbonyloxy groups of 1 to 4 carbon atoms,        branched or unbranched dialkylaminocarbonyloxy groups of 1 to 4        carbon atoms, branched or unbranched dialkylaminosulfonyloxy        groups of 1 to 4 carbon atoms, branched or unbranched alkylthio        groups of 1 to 4 carbon atoms, branched or unbranched        haloalkylthio groups of 1 to 4 carbon atoms, branched or        unbranched alkylsulfinyl groups of 1 to 4 carbon atoms, branched        or unbranched haloalkylsulfinyl groups of 1 to 4 carbon atoms,        branched or unbranched alkylsulfonyl groups of 1 to 4 carbon        atoms, branched or unbranched haloalkylsulfonyl groups of 1 to 4        carbon atoms, halogen atoms, cyano group, nitro group, phenyl        group optionally having substituent groups (the substituent        groups are the same as the above substituent groups), phenoxy        group optionally having substituent groups on the benzene ring        (the substituent groups are the same as the above substituent        groups) and benzyloxy group optionally having substituent groups        on the benzene ring (the substituent groups are the same as the        above substituent groups);    -   or said substituent groups being a group represented by the        formula (2):        wherein R₆ and R₇ are the same or different and each denotes a        hydrogen atom or a branched or unbranched alkyl group of 1 to 4        carbon atoms;    -   or said substituent groups being a group represented by the        formula (3):        wherein R₈, R₉ and R₁₀ are the same or different and each        denotes a hydrogen atom or a branched or unbranched alkyl group        of 1 to 4 carbon atoms;    -   said substituent groups substituting a hydrogen atom at 0 to 5        arbitrary positions of the phenyl group;    -   a group D is a hydrogen atom, a branched or unbranched alkyl        group of 1 to 4 carbon atoms, a branched or unbranched haloalkyl        group of 1 to 4 carbon atoms, an alkenyl group of 2 to 4 carbon        atoms, an alkynyl group of 2 to 4 carbon atoms, a branched or        unbranched alkoxy group of 1 to 4 carbon atoms, a cycloalkyl        group of 3 to 6 carbon atoms, a cyano group, a halogen atom, a        branched or unbranched alkoxycarbonyl group of 1 to 4 carbon        atoms, a branched or unbranched alkylthio group of 1 to 4 carbon        atoms, a branched or unbranched alkylsulfinyl group of 1 to 4        carbon atoms, a branched or unbranched alkylsulfonyl group of 1        to 4 carbon atoms, or a phenyl group optionally having        substituent groups (the substituent groups are the same as the        aforesaid substituent groups), said substituent groups        substituting a hydrogen atom at 0 to 5 arbitrary positions of        the phenyl group;    -   a group E is a hydrogen atom, a branched or unbranched alkyl        group of 1 to 4 carbon atoms, a cycloalkyl group of 3 to 6        carbon atoms, a halogen atom, or a phenyl group optionally        having substituent groups (the substituent groups are the same        as the aforesaid substituent groups), said substituent groups        substituting a hydrogen atom at 0 to 5 arbitrary positions of        the phenyl group;    -   groups R₁ and R₂ are the same or different and each denotes a        hydrogen atom, a halogen atom, a branched or unbranched alkyl        group of 1 to 4 carbon atoms, or a branched or unbranched        haloalkyl group of 1 to 4 carbon atoms;    -   a group R₃ is a hydrogen atom, a branched or unbranched alkyl        group of 1 to 4 carbon atoms, a branched or unbranched haloalkyl        group of 1 to 4 carbon atoms, an alkenyl group of 2 to 4 carbon        atoms, an alkynyl group of 2 to 4 carbon atoms, or a branched or        unbranched alkoxyalkyl group of 1 to 4 carbon atoms;    -   groups R₄ and R₅ are the same or different and each denotes a        hydrogen atom, a branched or unbranched alkyl group of 1 to 4        carbon atoms, a branched or unbranched haloalkyl group of 1 to 4        carbon atoms, a cycloalkyl group of 3 to 8 carbon atoms which        may be substituted with a branched or unbranched alkyl group of        1 to 4 carbon atoms, an alkenyl group of 2 to 4 carbon atoms, an        alkynyl group of 2 to 4 carbon atoms, a branched or unbranched        alkoxyalkyl group of 1 to 4 carbon atoms, a cyanomethyl group, a        substituted or unsubstituted amino group, or a phenyl group        optionally having substituent groups;    -   said substituent groups being the same as or different from one        another and selected from branched or unbranched alkyl groups of        1 to 4 carbon atoms, branched or unbranched haloalkyl groups of        1 to 4 carbon atoms, branched or unbranched alkoxy groups of 1        to 4 carbon atoms, branched or unbranched haloalkoxy groups of 1        to 4 carbon atoms, halogen atoms, cyano group and nitro group,        wherein said substituent groups substitute a hydrogen atom at 0        to 5 arbitrary positions of the phenyl group;    -   or groups R₄ and R₅ are each a benzyl group optionally having        substituent groups on the benzene ring;    -   said substituent groups being the same as or different from one        another and selected from branched or unbranched alkyl groups of        1 to 4 carbon atoms, branched or unbranched haloalkyl groups of        1 to 4 carbon atoms, branched or unbranched alkoxy groups of 1        to 4 carbon atoms, branched or unbranched haloalkoxy groups of 1        to 4 carbon atoms, halogen atoms, cyano group and nitro group,        wherein said substituent groups substitute a hydrogen atom at 0        to 5 arbitrary positions of the benzene ring;    -   or groups R₄ and R₅ are each an α- or β-phenethyl group        optionally having substituent groups on the benzene ring, said        substituent groups being selected from branched or unbranched        alkyl groups of 1 to 4 carbon atoms, branched or unbranched        haloalkyl groups of 1 to 4 carbon atoms, branched or unbranched        alkoxy groups of 1 to 4 carbon atoms, branched or unbranched        haloalkoxy groups of 1 to 4 carbon atoms, halogen atoms, cyano        group and nitro group, wherein said substituent groups        substitute a hydrogen atom at 0 to 5 arbitrary positions of the        benzene ring;    -   or groups R₄ and R₅ together form a five-membered or        six-membered aliphatic ring, wherein said ring may be        substituted with a group selected from branched or unbranched        alkyl groups of 1 to 4 carbon atoms, branched or unbranched        haloalkyl groups of 1 to 4 carbon atoms, branched or unbranched        alkoxy groups of 1 to 4 carbon atoms, branched or unbranched        haloalkoxy groups of 1 to 4 carbon atoms, halogen atoms, cyano        group and nitro group, and said ring may contain one or two        heteroatoms.

A substituted pyrazole hydrazide derivative according to the presentinvention has the above formula (1) in which R₄ is a hydrogen atom andR₅ is a substituted amino group —N(R₁₁,R₁₂), and is represented by thefollowing formula (4):

wherein:

-   -   n is 0 or 1;    -   each group A, D, E, R₁, R₂ and R₃ denotes independently the same        substituent groups as in the formula (1); and    -   groups R₁₁ and R₁₂ are the same or different and each denotes a        hydrogen atom, a branched or unbranched alkyl group of 1 to 4        carbon atoms, a branched or unbranched haloalkyl group of 1 to 4        carbon atoms, a branched or unbranched alkoxycarbonyl group of 1        to 4 carbon atoms, or a phenyl group optionally having        substituent groups, said substituent groups being the same as or        different from one another and selected from alkyl groups of 1        to 4 carbon atoms, haloalkyl groups of 1 to 4 carbon atoms,        alkoxy groups of 1 to 4 carbon atoms, haloalkoxy groups of 1 to        4 carbon atoms (these groups may be branched or unbranched),        halogen atoms, cyano group and nitro group, wherein said        substituent groups substitute a hydrogen atom at 0 to 5        arbitrary positions of the phenyl group.

A process for preparing substituted pyrazole derivatives of the formula(1) comprises reacting a pyrazole derivative of the formula (5) with ahaloalkyleneoxime ester derivative of the formula (6) to obtain apyrazole derivative ester of the formula (7):

and hydrolyzing the ester group of the pyrazole derivative ester of theformula (7) in the presence of a base to yield a carboxylic acidderivative of the formula (8) and reacting the carboxylic acidderivative with an amine R₄—NH—R₅ in the presence of a condensationagent:

wherein in the formulae (5) to (8), n is 0 or 1, a group Z is a halogenatom, a group R₁₃ is a methyl or ethyl group, and each group A, D, E,R₁, R₂, R₃, R₄ and R₅ denotes independently the same substituent groupsas in the formula (1).

A process for preparing the haloalkyleneoxime ester derivative of theformula (6) according to the present invention comprises allowing ahydroxylamine derivative of the formula (19) to act on a halopyruvatederivative of the formula (18) in the presence of a solvent, saidhydroxylamine derivative being used in 1 or more equivalents perequivalent of said halopyruvate derivative:

wherein n is 0 or 1, a group Z is a halogen atom, a group R₁₃ is amethyl or ethyl group, and each group R₁, R₂ and R₃ denotesindependently the same substituent groups as in the formula (1).

A herbicide composition according to the present invention comprises oneor more kinds of the substituted pyrazole derivatives of the formula (1)as active ingredients.

A herbicide composition according to the present invention comprises oneor more kinds of the substituted pyrazole derivatives of the formula (4)as active ingredients.

The inventive compound is a substituted pyrazole derivative preferablyrepresented by the following formula (1):

wherein:

-   -   n is 0 or 1; independently    -   a group A is a hydrogen atom, a branched or unbranched alkyl        group of 1 to 4 carbon atoms, a branched or unbranched haloalkyl        group of 1 to 4 carbon atoms, a cycloalkyl group of 3 to 6        carbon atoms, or a phenyl group substituted with 0 to 5        substituent groups (0 substituent group means an unsubstituted        phenyl group);    -   said substituent groups being the same as or different from one        another and selected from alkyl groups of 1 to 4 carbon atoms,        haloalkyl groups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4        carbon atoms, haloalkoxy groups of 1 to 4 carbon atoms,        alkylcarbonyloxy groups of 1 to 4 carbon atoms,        alkoxycarbonyloxy groups of 1 to 4 carbon atoms,        dialkylaminocarbonyloxy groups of 1 to 4 carbon atoms, alkylthio        groups of 1 to 4 carbon atoms, haloalkylthio groups of 1 to 4        carbon atoms, alkylsulfinyl groups of 1 to 4 carbon atoms,        haloalkylsulfinyl groups of 1 to 4 carbon atoms (these groups        may be linear or branched), halogen atoms, hydroxyl group, cyano        group, N-hydroxyimino group, N-methoxyimino group,        N,N-dimethylaminoimino group, phenyl group, phenoxy group and        benzyloxy group;    -   a group D is a hydrogen atom, a halogen atom, a branched or        unbranched alkyl group of 1 to 4 carbon atoms, a branched or        unbranched haloalkyl group of 1 to 4 carbon atoms, an alkynyl        group of 2 to 4 carbon atoms, a branched or unbranched alkoxy        group of 1 to 4 carbon atoms, an alkoxycarbonyl group of 1 to 4        carbon atoms, an alkylsulfinyl group of 1 to 4 carbon atoms or a        phenyl group;    -   a group E is a hydrogen atom, a halogen atom, a branched or        unbranched alkyl group of 1 to 4 carbon atoms or a phenyl group;    -   groups R₁ and R₂ are each a hydrogen atom or a methyl group;    -   a group R₃ is a hydrogen atom, a branched or unbranched alkyl        group of 1 to 4 carbon atoms, an alkenyl group of 2 to 4 carbon        atoms, an alkynyl group of 2 to 4 carbon atoms, a branched or        unbranched alkoxyalkyl group of 1 to 4 carbon atoms, a        fluoromethyl group or a benzyl group;    -   groups R₄ and R₅ together form a five-membered or six-membered        aliphatic ring which may contain 1 or 2 heteroatoms and which        may be substituted with an alkyl group of 1 to 4 carbon atoms,        or independently a group R₄ is a hydrogen atom or a branched or        unbranched alkyl group of 1 to 4 carbon atoms, and a group R₅ is        a hydrogen atom, a branched or unbranched alkyl group of 1 to 4        carbon atoms, a branched or unbranched haloalkyl group of 1 to 4        carbon atoms, a branched or unbranched cyanoalkyl group of 1 to        4 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms which        may be substituted with a branched or unbranched alkyl group of        1 to 4 carbon atoms, an alkenyl group of 2 to 4 carbon atoms, an        alkynyl group of 2 to 4 carbon atoms, a phenyl group, a benzyl        group, or an α- or β-phenethyl group optionally having a        (branched or unbranched) alkoxy group of 1 to 4 carbon atoms on        the benzene ring.

The inventive compound is a substituted pyrazole derivative having theformula (1) in which R₄ is a hydrogen atom and R₅ is a substituted aminogroup —N(R₁₁, R₁₂), and is represented by the following formula (4):

wherein:

-   -   n is 0 or 1;    -   each group A, D, E, R₁, R₂ and R₃ denotes independently the same        substituent groups as in the formula (1); and    -   groups R₁₁ and R₁₂ are the same or different and each denotes a        hydrogen atom, an alkyl group of 1 to 4 carbon atoms, a        haloalkyl group of 1 to 4 carbon atoms or an alkoxycarbonyl        group of 1 to 4 carbon atoms (these groups may be branched or        unbranched).

A herbicide composition according to the present invention comprises oneor more kinds of the above substituted pyrazoles preferably as activeingredients.

A herbicide composition according to the present invention comprises oneor more kinds of the substituted pyrazole hydrazide derivatives asactive ingredients.

DETAILED DESCRIPTION OF THE INVENTION

The substituted pyrazole derivatives (also referred to as “inventivecompounds”) are novel compounds showing sufficient harmless to importantcrops and having an excellent herbicidal activity, and possess astructure represented by the formula (1) or (4). They have a commonskeleton composed of a substituted pyrazole ring and an N-oxime acidamide. The substituted pyrazole derivative of the formula (4) is ahydrazide derivative of the compound of the formula (1). The inventivecompounds are illustrated hereinbelow as ones having specific groups,but are not limited thereto.

The scope of the present invention includes derivatives of the inventivecompounds having various substituent groups, salts (e.g., sodium salts,potassium salts, magnesium salts, calcium salts, aluminum salts, zincsalts), hydrates, solvates and crystal polymorphs of the compounds.Further, stereoisomers are possible when the inventive compounds containan asymmetric carbon (for example, when R₁ and R₂ in the formula (1) or(4) are different each other). The inventive compounds encompass all thepossible isomers and mixtures containing two or more isomers inarbitrary proportions.

Hereinbelow, detailed structures of the inventive compounds (1) and (4),production processes, herbicidal effects, formulations and applicationmethods thereof will be described in the order named.

Substituted Pyrazole Derivatives

The inventive compounds are substituted pyrazole derivatives comprisinga substituted pyrazole ring and an N-oxime acid amide as illustrated inthe formula (1), and hydrazide derivatives thereof (represented by theformula (4)) In the formulae (1) and (4), n is 0 or 1. In either case,the acid amides (1) and hydrazide derivatives thereof (4) of the presentinvention may contain a hydrogen atom and other groups described belowas substituent groups A, D, E, R₁ to R₅, R₁₁ and R₁₂.

The group A in the formula (1) is a hydrogen atom, a branched orunbranched alkyl group of 1 to 4 carbon atoms, a branched or unbranchedhaloalkyl group of 1 to 4 carbon atoms, a cycloalkyl group of 3 to 6carbon atoms, or a phenyl group optionally having one or moresubstituent groups listed below.

The substituent groups of the phenyl group may be the same as ordifferent from one another and be selected from branched or unbranchedalkyl groups of 1 to 4 carbon atoms, branched or unbranched haloalkylgroups of 1 to 4 carbon atoms, branched or unbranched alkoxy groups of 1to 4 carbon atoms, branched or unbranched haloalkoxy groups of 1 to 4carbon atoms, branched or unbranched alkylcarbonyloxy groups of 1 to 4carbon atoms, cycloalkylcarbonyloxy groups of 3 to 6 carbon atoms,branched or unbranched alkoxycarbonyloxy groups of 1 to 4 carbon atoms,branched or unbranched dialkylaminocarbonyloxy groups of 1 to 4 carbonatoms, branched or unbranched dialkylaminosulfonyloxy groups of 1 to 4carbon atoms, branched or unbranched alkylthio groups of 1 to 4 carbonatoms, branched or unbranched haloalkylthio groups of 1 to 4 carbonatoms, branched or unbranched alkylsulfinyl groups of 1 to 4 carbonatoms, branched or unbranched haloalkylsulfinyl groups of 1 to 4 carbonatoms, branched or unbranched alkylsulfonyl groups of 1 to 4 carbonatoms, branched or unbranched haloalkylsulfonyl groups of 1 to 4 carbonatoms, halogen atoms, hydroxyl group, cyano group, nitro group, phenylgroup optionally having one or more substituent groups (thesesubstituent groups are the same as the aforesaid substituent groups),phenoxy group optionally having one or more substituent groups on thebenzene ring (these substituent groups are the same as the aforesaidsubstituent groups) and benzyloxy group optionally having one or moresubstituent groups on the benzene ring (these substituent groups are thesame as the aforesaid substituent groups).

The aforesaid substituent groups of the phenyl group may be otherwise agroup represented by the formula (2):

wherein R₆ and R₇ are the same or different and each denotes a hydrogenatom or a branched or unbranched alkyl group of 1 to 4 carbon atoms.

Alternatively, the substituent groups of the phenyl group may be a grouphaving the formula (3):

wherein R₈, R₉ and R₁₀ are the same or different and each denotes ahydrogen atom or a branched or unbranched alkyl group of 1 to 4 carbonatoms.

These exemplified substituent groups may substitute a hydrogen atom at 0to 5 arbitrary positions of the phenyl group.

Specific examples of the above-mentioned groups are listed below withoutlimiting the scope of the invention.

The branched or unbranched alkyl groups of 1 to 4 carbon atoms includemethyl, ethyl, propyl and butyl groups, and isomer groups thereof.

The branched or unbranched haloalkyl groups of 1 to 4 carbon atomsinclude fluoromethyl, difluoromethyl, trifluoromethyl, dichloroethyl andbromopropyl groups, and isomer groups thereof.

The cycloalkyl groups of 3 to 6 carbon atoms include cyclopropyl,cyclobutyl, cyclopentyl and cyclohexyl groups.

The “phenyl group optionally having one or more substituent groups”given as an exemplary group A in the formula (1) refers to a phenylgroup substituted with same or different substituent group(s) at 0 to 5arbitrary positions. Examples of the substituent groups include branchedor unbranched alkyl groups of 1 to 4 carbon atoms, branched orunbranched haloalkyl groups of 1 to 4 carbon atoms, branched orunbranched alkoxy groups of 1 to4 carbon atoms, branched or unbranchedhaloalkoxy groups of 1 to 4 carbon atoms, branched or unbranchedalkylcarbonyloxy groups of 1 to 4 carbon atoms, cycloalkylcarbonyloxygroups of 3 to 6 carbon atoms, branched or unbranched alkoxycarbonyloxygroups of 1 to 4 carbon atoms, branched or unbrancheddialkylaminocarbonyloxy groups of 1 to 4 carbon atoms, branched orunbranched dialkylaminosulfonyloxy groups of 1 to 4 carbon atoms,branched or unbranched alkylthio groups of 1 to 4 carbon atoms, branchedor unbranched haloalkylthio groups of 1 to 4 carbon atoms, branched orunbranched alkylsulfinyl groups of 1 to 4 carbon atoms, branched orunbranched haloalkylsulfinyl groups of 1 to 4 carbon atoms, branched orunbranched alkylsulfonyl groups of 1 to 4 carbon atoms, branched orunbranched haloalkylsulfonyl groups of 1 to 4 carbon atoms halogenatoms, hydroxyl group, cyano group and nitro group. Specific examples ofthe alkyl groups and haloalkyl groups include, but not limited to, thegroups described hereinabove.

The branched or unbranched alkoxy groups of 1 to 4 carbon atoms includemethoxy, ethoxy, propoxy and butoxy groups, and isomer groups thereof.

The branched or unbranched haloalkoxy groups of 1 to 4 carbon atomsinclude monofluoromethoxy and chloropropoxy groups, and isomer groupsthereof.

The branched or unbranched alkylcarbonyloxy groups of 1 to 4 carbonatoms include methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy andbutylcarbonyloxy groups.

The cycloalkylcarbonyloxy groups of 3 to 6 carbon atoms includecyclopentylcarbonyloxy and cyclohexylcarbonyloxy groups.

The branched or unbranched alkoxycarbonyloxy groups of 1 to 4 carbonatoms include methoxycarbonyloxy, ethoxycarbonyloxy, propoxycarbonyloxyand butoxycarbonyloxy groups.

The branched or unbranched dialkylaminocarbonyloxy groups of 1 to 4carbon atoms include dimethylaminocarbonyloxy anddiethylaminocarbonyloxy groups.

The branched or unbranched dialkylaminosulfonyloxy groups of 1 to 4carbon atoms include dimethylaminosulfonyloxy anddiethylaminosulfonyloxy groups.

The branched or unbranched alkylthio groups of 1 to 4 carbon atomsinclude methylthio, ethylthio, propylthio and butylthio groups, andisomer groups thereof.

The branched or unbranched haloalkylthio groups of 1 to 4 carbon groupsinclude monochloromethylthio and trifluoromethylthio groups.

The branched or unbranched alkylsulfinyl groups of 1 to 4 carbon atomsinclude methylsulfinyl, ethylsulfinyl, propylsulfinyl and butylsulfinylgroups, and isomer groups thereof.

The branched or unbranched haloalkylsulfinyl groups of 1 to 4 carbonatoms include monochloromethylsulfinyl and monofluoromethylsulfinylgroups.

The branched or unbranched alkylsulfonyl groups of 1 to 4 carbon atomsinclude methylsulfonyl, ethylsulfonyl, propylsulfonyl and butylsulfonylgroups, and isomer groups thereof.

The branched or unbranched haloalkylsulfonyl groups of 1 to 4 carbonatoms include monobromomethylsulfonyl and monofluoromethylsulfonylgroups.

The halogen atoms include fluorine, chlorine, bromine and iodine atoms.

The arbitrary substituent groups on the phenyl group may each be aphenyl group optionally having further one or more substituent groups(these substituent groups are the same as the aforesaid substituentgroups), a phenoxy group optionally having one or more substituentgroups on the benzene ring (these substituent groups are the same as theaforesaid substituent groups), or a benzyloxy group optionally havingone or more substituent groups on the benzene ring (these substituentgroups are the same as the aforesaid substituent groups). Specificexamples of such substituted phenyl groups (having one or moresubstituent groups on the benzene ring) include methylphenyl group,chlorophenyl group, dichlorophenyl group,3(1-(chlorobenzyloxyimino)-ethyl)phenyl group, 3-(benzyloxy)phenylgroup, 3-(methylbenzyloxy)phenyl group, 3-(chlorobenzyloxy)phenyl group,3-(cyanobenzyloxy)phenyl group, 3-(dimethylbenzyloxy)phenyl group,3-(dichlorobenzyloxy)phenyl group, 3-(pyridylmethoxy)phenyl group,3-(benzoyloxy)phenyl group, 3-(chlorobenzoyloxy)phenyl group, benzylgroup, phenoxymethyl group, methylphenoxymethyl group, phenylthiomethylgroup, methylphenylthiomethyl group, 1-phenoxyethyl group,1-(methylphenoxy)ethyl group, 1-phenylthioethyl group,1-(methylphenylthio)ethyl group, phenoxy group, 2-methylphenoxy group,3-methylphenoxy group, 4-methylphenoxy group, 2-chlorophenoxy group,3-chlorophenoxy group, 4-chlorophenoxy group, 2-trifluoromethylphenoxygroup, 2,5-dimethylphenoxy group, 2,5-dichlorophenoxy group,2-chloro-5-trifluoromethylphenoxy group, phenylthio group,2-methylphenylthio group, benzyloxy group, 2-methylbenzyloxy group,3-methylbenzyloxy group, 4-methylbenzyloxy group, 2-chlorobenzyloxygroup, 3-chlorobenzyloxy group, 4-chlorobenzyloxy group,2-trifluoromethylbenzyloxy group, 2,5-dimethylbenzyloxy group,2,5-dichlorobenzyloxy group, 2-chloro-5-trifluoromethylbenzyloxy group,benzylthio group, 2-methylbenzylthio group, benzyloxyiminomethyl group,2-methylbenzyloxyiminomethyl group, 3-methylbenzyloxyiminomethyl groupand 4-methylbenzyloxyiminomethyl group.

Further, groups represented by the following formula (2) or (3) are alsoavailable as the arbitrary substituent groups on the phenyl group:

wherein R₆ and R₇ may be the same or different and each denotes ahydrogen atom or a branched or unbranched alkyl group of 1 to 4 carbonatoms;

wherein R₈, R₉ and R₁₀ may be the same or different and each denotes ahydrogen atom or a branched or unbranched alkyl group of 1 to 4 carbonatoms.

The branched or unbranched alkyl groups of 1 to 4 carbon atoms for theabove groups (R₆, R₇, R₈, R₉ and R₁₀) include the alkyl groups listedabove, but are not limited thereto.

Of the groups A listed above, particularly preferred are a hydrogenatom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butylgroup, t-butyl group, trifluoromethyl group, cyclopropyl group,cyclobutyl group, cyclopentyl group, cyclohexyl group, phenyl group,2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group,2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group,2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group,2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenylgroup, 2,6-difluorophenyl group, 3,4-difluorophenyl group,3,5-difluorophenyl group, 2,5-dichlorophenyl group,2-fluoro-4-chlorophenyl group, 3-fluoro-4-chlorophenyl group,4-fluoro-2-chlorophenyl group, 4-fluoro-3-bromophenyl group,4-cyanophenyl group, 2-methylphenyl group, 3-methylphenyl group,4-methylphenyl group, 3,4-dimethylphenyl group, 3-fluoro-4-methylphenylgroup, 4-fluoro-3-methylphenyl group, 2-fluoro-3-trifluoromethylphenylgroup, 2-fluoro-4-trifluoromethylphenyl group,2-fluoro-5-trifluoromethylphenyl group, 3-fluoro-4-trifluoromethylphenylgroup, 3-fluoro-5-trifluoromethylphenyl group,4-fluoro-2-trifluoromethylphenyl group, 4-fluoro-3-trifluoromethylphenylgroup, 4-isopropylphenyl group, 4-trifluoromethylphenyl group,4-hydroxyphenyl group, 4-acetyloxyphenyl group,dimethylaminocarbonyloxyphenyl group, dimethylaminosulfinyloxyphenylgroup, 4-methylthiophenyl group, 4-methylsulfinylphenyl group,4-trifluoromethylthiophenyl group, 4-methoxyphenyl group,2,3-dimethoxyphenyl group, 3-fluoro-4-methoxyphenyl group,4-fluoro-3-methoxyphenyl group, 2-chloro-4-methoxyphenyl group,3-chloro-4-methoxyphenyl group, 4-difluoromethoxyphenyl group,4-trifluoromethoxyphenyl group, 4-(2,1,1-trifluoroethoxy)phenyl group,2-difluoromethoxy-4-methoxyphenyl group, 3,5-difluoro-4-methoxyphenylgroup, 4-phenylphenyl group, 3-phenoxyphenyl group, 4-phenoxyphenylgroup, 4-benzyloxyphenyl group, 4-(N-hydroxyimino)phenyl group,4-(N-methoxyimino)phenyl group and 4-(N,N-dimethylaminoxyimino)phenylgroup.

The group D in the formula (1) is a hydrogen atom, a branched orunbranched alkyl group of 1 to 4 carbon atoms, a branched or unbranchedhaloalkyl group of 1 to 4 carbon atoms, an alkenyl group of 2 to 4carbon atoms, an alkynyl group of 2 to 4 carbon atoms, a branched orunbranched alkoxy group of 1 to 4 carbon atoms, a cycloalkyl group of 3to 6 carbon atoms, a cyano group, a halogen atom, a branched orunbranched alkoxycarbonyl group of 1 to 4 carbon atoms, a branched orunbranched alkylthio group of 1 to 4 carbon atoms, a branched orunbranched alkylsulfinyl group of 1 to 4 carbon atoms, a branched orunbranched alkylsulfonyl group of 1 to 4 carbon atoms, or a phenyl groupoptionally having one or more substituent groups (these substituentgroups are the same as the aforesaid substituent groups). Theexemplified substituent groups may substitute a hydrogen atom at 0 to 5arbitrary positions of the phenyl group.

The alkenyl groups of 2 to 4 carbon atoms include vinyl, propenyl andbutenyl groups. For the latter two groups, isomer groups based on thedouble bond are possible.

The alkynyl groups of 2 to 4 carbon atoms include linear or branchedethynyl, propynyl and butynyl groups, and isomer groups thereof.

The branched or unbranched alkoxycarbonyl groups of 1 to 4 carbon atomsinclude methoxycarbonyl, ethoxycarbonyl and propoxycarbonyl groups.

Specific examples of the other groups as the group D include theaforesaid groups, but are not limited thereto.

Of the groups for D listed above, preferred are a hydrogen atom,chlorine atom, methyl group, ethyl group, ethynyl group, trifluoromethylgroup, methylsulfinyl group, ethoxycarbonyl group and phenyl group.

The group E in the formula (1) is a hydrogen atom, a branched orunbranched alkyl group of 1 to 4 carbon atoms, a cycloalkyl group of 3to 6 carbon atoms, a halogen atom, or a phenyl group optionally havingone or more substituent groups (these substituent groups are the same asthe aforesaid substituent groups). The exemplified substituent groupsmay substitute a hydrogen atom at 0 to 5 arbitrary positions of thephenyl group. Specific examples of these groups include those mentionedhereinabove, but are not limited thereto.

Of the groups for E listed above, preferred are a hydrogen atom, halogenatom, branched or unbranched alkyl group of 1 to 4 carbon atoms andphenyl group.

The groups R₁ and R₂ may be the same or different each other and eachdenotes a hydrogen atom, a halogen atom, a branched or unbranched alkylgroup of 1 to 4 carbon atoms, or a branched or unbranched haloalkylgroup of 1 to 4 carbon atoms. Specific examples of these groups includethose mentioned hereinabove, but are not limited thereto. Of the groupslisted as R₁ and R₂, preferred are a hydrogen atom and methyl group.Particularly preferably, the groups R₁ and R₂ are both hydrogen atoms.

The group R₃ is a hydrogen atom, a branched or unbranched alkyl group of1 to 4 carbon atoms, a branched or unbranched haloalkyl group of 1 to 4carbon atoms, an alkenyl group of 2 to 4 carbon atoms, an alkynyl groupof 2 to 4 carbon atoms, or a branched or unbranched alkoxyalkyl group of1 to 4 carbon atoms. Specific examples of these groups are as describedhereinabove, but are not limited thereto. Of the groups for R₃,preferred are a hydrogen atom, branched or unbranched alkyl group of 1to 4 carbon atoms, alkenyl group of 2 to 4 carbon atoms, alkynyl groupof 2 to 4 carbon atoms, branched or unbranched alkoxyalkyl group of 1 to4 carbon atoms, fluoromethyl group and benzyl group.

The groups R₄ and R₅ may be the same or different each other and eachdenotes a hydrogen atom, a branched or unbranched alkyl group of 1 to 4carbon atoms, a branched or unbranched haloalkyl group of 1 to 4 carbonatoms, a cycloalkyl group of 3 to 8 carbon atoms which may besubstituted with a branched or unbranched alkyl group of 1 to 4 carbonatoms, an alkenyl group of 2 to 4 carbon atoms, an alkynyl group of 2 to4 carbon atoms, a branched or unbranched alkoxyalkyl group of 1 to 4carbon atoms, a substituted or unsubstituted amino group, a cyanomethylgroup, or a phenyl group substituted with 0 to 5 arbitrary substituentgroups mentioned as hereunder. Such substituent groups may be the sameas or different from one another and are selected from branched orunbranched alkyl groups of 1 to 4 carbon atoms, branched or unbranchedhaloalkyl groups of 1 to 4 carbon atoms, branched or unbranched alkoxygroups of 1 to 4 carbon atoms, branched or unbranched haloalkoxy groupsof 1 to 4 carbon atoms, halogen atoms, cyano group and nitro group. Theexemplified substituent groups may substitute a hydrogen atom at 0 to 5arbitrary positions of the phenyl group.

Further, the groups R₄ and R₅ may each be a benzyl group optionallyhaving one or more substituent groups on the benzene ring. Thesubstituent groups may be the same as or different from one another andare selected from branched or unbranched alkyl groups of 1 to 4 carbonatoms, branched or unbranched haloalkyl groups of 1 to 4 carbon atoms,branched or unbranched alkoxy groups of 1 to 4 carbon atoms, branched orunbranched haloalkoxy groups of 1 to 4 carbon atoms, halogen atoms,cyano group and nitro group. The exemplified substituent groups maysubstitute a hydrogen atom at 0 to 5 arbitrary positions of the benzenering of the benzyl group.

Furthermore, the groups R₄ and R₅ may each be an α- or β-phenethyl groupoptionally having one or more substituent groups on the benzene ring.The substituent groups are selected from branched or unbranched alkylgroups of 1 to 4 carbon atoms, branched or unbranched haloalkyl groupsof 1 to 4 carbon atoms, branched or unbranched alkoxy groups of 1 to 4carbon atoms, branched or unbranched haloalkoxy groups of 1 to 4 carbonatoms, halogen atoms, cyano group and nitro group. The exemplifiedsubstituent groups may substitute a hydrogen atom at 0 to 5 arbitrarypositions of the benzene ring of the α- or β-phenethyl group.

Examples of the branched or unbranched alkyl groups of 1 to 4 carbonatoms, branched or unbranched haloalkyl groups of 1 to 4 carbon atoms,alkenyl groups of 2 to 4 carbon atoms, alkynyl groups of 2 to 4 carbonatoms, branched or unbranched alkoxyalkyl groups of 1 to 4 carbon atoms,branched or unbranched haloalkyl groups of 1 to 4 carbon atoms, halogenatoms and substituted phenyl groups include the groups describedhereinabove, but are not limited thereto.

Examples of the substituted or unsubstituted amino group include aminogroup and substituted amino groups such as dimethylamino group,diethylamino group, dipropylamino group, dibutylamino group,ethylmethylamino group, diphenylamino group, anilino group, anisidinogroup, phenetidino group, toluidino group, xylidino group,methoxycarbonylamino group, cyclopropylamino group and ethynylaminogroup.

Examples of the cycloalkyl groups of 3 to 8 carbon atoms which may besubstituted with a branched or unbranched alkyl group of 1 to 4 carbonatoms include cyclopropyl.group, cyclobutyl group, cyclopentyl group,cyclohexyl group, cycloheptyl group, cyclooctyl group, and thesealicyclic groups substituted with a branched or unbranched alkyl groupof 1 to 4 carbon atoms.

Of the groups listed above for R₄, a hydrogen atom, methyl group andethyl group are preferred. Of the groups listed above for R₅, preferredare a hydrogen atom, branched or unbranched alkyl group of 1 to 4 carbonatoms, branched or unbranched haloalkyl group of 1 to 4 carbon atoms,branched or unbranched cyanoalkyl group of 1 to 4 carbon atoms,cycloalkyl group of 3 to 6 carbon atoms which may be substituted with analkyl group, substituted or unsubstituted phenyl group, substituted orunsubstituted benzyl group and substituted or unsubstituted phenethylgroup.

Furthermore, the groups R₄ and R₅ may together form a five-membered orsix-membered aliphatic ring. The ring may contain one or twoheteroatoms. The heteroatoms in the aliphatic ring include nitrogen,oxygen, sulfur, phosphorous and arsenic. The five-membered orsix-membered ring may be substituted with a group selected from alkylgroups of 1 to 4 carbon atoms, branched or unbranched haloalkyl groupsof 1 to 4 carbon atoms, branched or unbranched alkoxy groups of 1 to 4carbon atoms, haloalkoxy groups of 1 to 4 carbon atoms, halogen atoms,cyano group and nitro group.

In a particularly preferable embodiment of the inventive compounds, R₄and R₅ together form a heteroalicyclic group such as a five-membered orsix-membered ring containing one nitrogen atom, or a six-membered ringcontaining one nitrogen atom and one oxygen or sulfur atom (e.g.,Compounds Nos. 118-122 in Table 1 of Examples presented later).

Specific examples of the group —N(R₄R₅) in the formula (1) are givenbelow, including the cases where R₄ and R₅ together form a five-memberedor six-membered aliphatic ring substituted with an alkyl group of 1 to 4carbon atoms or the like. In the formulae given below, Me, Et, Pr, Bu,i, t, pen and hex denote methyl, ethyl, propyl, butyl, iso, tertiary,pentyl and hexyl, respectively.

PREFERRED EMBODIMENTS OF THE INVENTION

Table 1 lists Compounds Nos. 1 to 124 synthesized in Examples (describedlater) as typical examples of the substituted pyrazole derivatives ofthe formula (1) according to the present invention. However, theinventive compounds are not limited thereto.

When R₄ is a hydrogen atom and R₅ is a substituted amino group—N(R₁₁,R₁₂) in reference to the formula (1), in particular, theinventive compound is a substituted pyrazole hydrazide derivativerepresented by the formula (4):

wherein:

-   -   n is 0 or 1;    -   groups A, D, E, R₁, R₂ and R₃ each denote the same substituent        groups as in the formula (1); and groups R₁₁ and R₁₂ may be the        same or different and each denotes a hydrogen atom, a branched        or unbranched alkyl group of 1 to 4 carbon atoms, a branched or        unbranched haloalkyl group of 1 to 4 carbon atoms, a branched or        unbranched alkoxycarbonyl group of 1 to 4 carbon atoms, or a        phenyl group optionally having one or more substituent groups        listed below. The substituent groups may be the same as or        different from one another and is selected from branched or        unbranched alkyl groups of 1 to 4 carbon atoms, branched or        unbranched haloalkyl groups of 1 to 4 carbon atoms, branched or        unbranched alkoxy groups of 1 to 4 carbon atoms, branched or        unbranched haloalkoxy groups of 1 to 4 carbon atoms, halogen        atoms, cyano group and nitro group. The exemplified substituent        groups may substitute a hydrogen atom at 0 to 5 arbitrary        positions of the phenyl group. Specific examples of the above        groups are as described hereinabove, but are not limited        thereto.

In the substituted pyrazole derivatives of the formula (4), it ispreferable that the group A be a phenyl group substituted with 0 to 5substituent groups (0 substituent group means an unsubstituted phenylgroup), the group D be a group selected from branched or unbranchedalkyl groups of 1 to 4 carbon atoms, cycloalkyl groups of 3 to 6 carbonatoms and halogen atoms, the group E be a hydrogen atom or a branched orunbranched alkyl group of 1 to 4 carbon atoms, the groups R₁ and R₂ behydrogen atoms, the group R₃ be a group selected from branched orunbranched alkyl groups of 1 to 4 carbon atoms, alkenyl groups of 2 to 4carbon atoms, alkynyl groups of 2 to 4 carbon atoms and branched orunbranched alkoxyalkyl groups of 1 to 4 carbon atoms, and the groups R₁₁and R₁₂ be the same or different and selected from a hydrogen atom,branched or unbranched alkyl groups of 1 to 4 carbon atoms, branched orunbranched haloalkyl, groups of 1 to 4 carbon atoms and branched orunbranched cyanoalkyl groups of 1 to 4 carbon atoms.

Compounds No. 123 and 124 listed in Table 1 of Examples (presentedlater) are typical examples of the substituted pyrazole derivatives ofthe formula (4). However, the inventive compounds are not limitedthereto.

Production Process for Substituted Pyrazole Derivatives

A production process for the inventive compounds will be describedhereinbelow. To produce the inventive compound (1), the followingreaction steps are carried out:

Step (a): A pyrazole derivative of the formula (5) is reacted with ahaloalkyleneoxime ester derivative (i.e. oxime derivative ofhalopyruvate) of the formula (6) in the presence of a base to give anester derivative of the formula (7):Step (a):

wherein Z is a halogen atom and R₁₃ is a methyl or ethyl group.

Step (b): An ester moiety of the ester derivative (formula 7) ishydrolyzed with a base to yield a carboxylic acid derivative representedby the formula (8).

Step (c): The carboxylic acid derivative is reacted with an amineR₄—NH—R₅ in the presence of a condensation agent to form the inventivecompound (formula 1):Step (b): Step (c):

wherein R₄ and R₅ denote the same groups-as described above.

Exemplary condensation agents for use in the Step (c) includecarbonyldiimidazole, thionyldiimidazole, dicarboxycarbodiimide and1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride.

Some types of the amines can act on the ester derivative of the formula(7) to directly-synthesize the inventive compound of the formula (1).

Exemplary bases employed in the reaction between the pyrazole derivativeof the formula (5) and the haloalkyleneoxime ester derivative of theformula (6) include inorganic bases such as sodium hydride, sodiumhydrogencarbonate, sodium carbonate, potassium carbonate and cesiumcarbonate, and organic bases such as triethylamine and1,8-diazabicyclo(5,4,0)-undeca-7-ene (DBU).

With respect to the amounts of the reagents subjected to the reaction,about 1 to 5 equivalents, preferably 1 to 3 equivalents of thehaloalkyleneoxime ester derivative of the formula (6), and about 1 to 5equivalents, preferably 1 to 3 equivalents of the base are used perequivalent of the pyrazole derivative represented by the formula (5).

In the above reaction, a solvent is usually used. The solventsemployable include ethers such as diethylether, 1,2-dimethoxyethane,tetrahydrofuran, ethylene oxide and 1,4-dioxane; acid amides such asN,N-dimethylformamide and N-methylpyrrolidone; ketones such as acetone,methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; andacetonitrile.

The reaction temperature and reaction time in the Step (a) are typicallyabout 0 to 150° C., preferably 10 to 100° C., and 10 minutes to 24 hoursrespectively. The reaction may be followed by conventional treatmentsand purification by column chromatography, recrystallization or the likeas required to prepare the objective compound.

Exemplary bases employable in the Step (b) include lithium hydroxide,potassium hydroxide and sodium hydroxide.

With respect to the amounts of the condensation agent subjected to thereaction, about 1 to 5 equivalents, preferably 1 to 3 equivalents areused, and also about 1 to 5 equivalents, preferably 1 to 3 equivalentsof the base are used per equivalent of the ester derivative representedby the formula (7).

In the above reaction, a mixture of water and an alcohol solvent isusually used. The solvents employable include methanol, ethanol,propanol and butanol. The solvent and water are used in equal amounts.

After the reaction, the reaction mixture may be treated by aconventional method, and the reaction product may be separated by columnchromatography, recrystallization or the like as required.

The reaction temperature and reaction time in the Step (c) are typicallyabout 0 to 100° C., preferably 10 to 80° C., and 10 minutes to 24 hoursrespectively.

The substituted pyrazole ring represented by the formula (5) may besynthesized from various pyrazole derivatives having the substituentgroups. Exemplary synthesis processes will be given below for thepyrazole rings in which the groups D and E are hydrogen atoms or aresubstituted, or in which the group D is a halogen atom.

The substituted pyrazole ring of the formula (5) in which E is ahydrogen atom may be obtained by reacting α-formyl ketone of thefollowing formula (9) with hydrazine hydrate (Step (d)). It also resultsfrom reaction of an enamine derivative of the formula (10) withhydrazine hydrate (Step (e)).

With respect to the amounts of the reagents subjected to the reaction,about 1 to 5 equivalents of the hydrazine hydrate is used per equivalentof the α-formyl ketone of the formula (9) or the enamine derivative ofthe formula (10).

In the above reaction, a solvent is usually used. The solventsemployable include ethers such as diethylether, 1,2-dimethoxyethane andtetrahydrofuran; acid amides such as N,N-dimethylformamide andN-methylpyrrolidone; alcohols such as methanol and ethanol; organicacids such as acetic acid; and aromatic hydrocarbons such as benzene andtoluene.

The reaction temperature and reaction time in the Step (d) are typicallyabout 0 to 150° C. and 10 minutes to 24 hours, respectively. Thereaction may be followed by a conventional treatment and purification bycolumn chromatography, recrystallization or the like as required toprepare the objective compound.

The α-formyl ketone represented by the formula (9) may be obtained byClaisen condensation between a ketone derivative of the formula (11) anda formate HCOOR¹⁴ (wherein R¹⁴ is a methyl or ethyl group) in thepresence of a base (Step (f))Step (f):

Exemplary bases employable in the above reaction include sodium hydride,sodium methylate and sodium ethylate.

With respect to the amounts of the reagents subjected to the reaction,about 1 to 20 equivalents of the formate and about 1 to 2 equivalents ofthe base are used per equivalent of the ketone derivative represented bythe formula (11).

In the above reaction, a solvent is usually used. Employable solventsinclude formates. The solvent may be optionally diluted with an ethersuch as diethylether, 1,2-dimethoxyethane or tetrahydrofuran.

The reaction temperature and reaction time in the Step (f) are typicallyabout 0 to 100° C. and 10 minutes to 24 hours, respectively. Thereaction may be followed by a conventional treatment and purification bycolumn chromatography, recrystallization or the like as required toprepare the objective compound.

The enamine derivative of the formula (10) may be obtained by reacting aketone derivative of the formula (11) with N,N-dimethylformamidedimethylacetal (Step (g))Step (g):

With respect to the amounts of the reagents subjected to the reaction, 1to 10 equivalents of the N,N-dimethylformamide dimethylacetal is usedper equivalent of the ketone derivative represented by the formula (11).

In the above reaction, a solvent is usually used. Exemplary solventsinclude aromatic hydrocarbons such as benzene and toluene; and etherssuch as 1,2-dimethoxyethane and tetrahydrofuran.

The reaction temperature and reaction time in the Step (g) are typicallyabout 0 to 150° C. and 10 minutes to 24 hours, respectively. Thereaction may be followed by a conventional treatment and purification bycolumn chromatography, recrystallization or the like as required toprepare the objective compound.

The substituted pyrazole ring of the formula (5) in which E is asubstituent group may be obtained by reacting a diketone derivative ofthe following formula (12) with hydrazine hydrate (Step (h)).Step (h):

With respect to the amounts of the reagents subjected to the reaction,about 1 to 5 equivalents of the hydrazine hydrate is used per equivalentof the ketone derivative of the formula (12).

In the above reaction, a solvent is usually used. The solventsemployable include ethers such as diethylether, 1,2-dimethoxyethane andtetrahydrofuran; acid amides such as N,N-dimethylformamide andN-methylpyrrolidone; alcohols such as methanol and ethanol; organicacids such as acetic acid; and aromatic hydrocarbons such as benzene andtoluene.

The reaction temperature and reaction time in the Step (h) are typicallyabout 0 to 150° C. and 10 minutes to 24 hours, respectively. Thereaction may be followed by a conventional treatment and purification bycolumn chromatography, recrystallization or the like as required toprepare the objective compound.

The ketone derivative represented by the formula (12) may be obtained byClaisen condensation between a ketone derivative of the formula (11) anda carboxylate in the presence of a base (Step (i)). R₁₅ is a C₁₋₄ alkylgroup.Step (i):

Exemplary bases employable in the above reaction include sodium hydride,sodium methylate and sodium ethylate.

With respect to the amounts of the reagents subjected to the reaction,about 1 to 20 equivalents of the carboxylate and about 1 to 2equivalents of the base are used per equivalent of the ketone derivativerepresented by the formula (11).

In the above reaction, a solvent is usually used. Exemplary solventsinclude ethers such as diethylether, 1,2-dimethoxyethane andtetrahydrofuran; and acid amides such as N,N-dimethylformamide andN-methylpyrrolidone.

The reaction temperature and reaction time in the Step (i) are typicallyabout 0 to 100° C. and 10 minutes to 24 hours, respectively. Thereaction may be followed by a conventional treatment and purification bycolumn chromatography, recrystallization or the like as required toprepare the objective compound.

The substituted pyrazole ring of the formula (5) in which D and E areboth hydrogen atoms may be obtained by reacting an enamine derivative ofthe following formula (13) with hydrazine hydrate (Step (j)) to preparea pyrazole derivative of the formula (5) in which D and E are bothhydrogen atoms.Step (j):

With respect to the amounts of the reagents subjected to the reaction,about 1 to 5 equivalents of the hydrazine hydrate is used per equivalentof the enamine derivative of the formula (13).

In the above reaction, a solvent is usually used. The solventsemployable include ethers such as diethylether, 1,2-dimethoxyethane andtetrahydrofuran; acid amides such as N,N-dimethylformamide andN-methylpyrrolidone; alcohols such as methanol and ethanol; organicacids such as acetic acid; and aromatic hydrocarbons such as benzene andtoluene.

The reaction temperature and reaction time in the Step (j) are typicallyabout 0 to 150° C. and 10 minutes to 24 hours, respectively. Thereaction may be followed by a conventional treatment and purification bycolumn chromatography, recrystallization or the like as required toprepare the objective compound.

The substituted pyrazole ring of the formula (5) in which D is ahydrogen atom may be obtained by reacting a diketone derivative of thefollowing formula (14) with hydrazine hydrate (Step (k)Step (k):

With respect to the amounts of the reagents subjected to the reaction,about 1 to 5 equivalents of the hydrazine hydrate is used per equivalentof the diketone derivative of the formula (14).

In the above reaction, a solvent is usually used. The solventsemployable include ethers such as diethylether, 1,2-dimethoxyethane andtetrahydrofuran; acid amides such as N,N-dimethylformamide andN-methylpyrrolidone; and aromatic hydrocarbons such as benzene andtoluene.

The reaction temperature and reaction time in the Step (k) are typicallyabout 0 to 150° C. and 10 minutes to 24 hours, respectively. Thereaction may be followed by a conventional treatment and purification bycolumn chromatography, recrystallization or the like as required toprepare the objective compound.

The diketone derivative represented by the formula (14) may be obtainedby Claisen condensation between a ketone derivative of the formula (15)and a carboxylate in the presence of a base (Step (1)). R₁₆ is a C₁₋₄alkyl group.Step (l):

With respect to the amounts of the reagents subjected to the reaction,about 1 to 20 equivalents of the carboxylate and about 1 to 2equivalents of the base are used per equivalent of the ketone derivativerepresented by the formula (14).

Exemplary bases employable in the above reaction include sodium hydride,sodium methylate and sodium ethylate.

In the above reaction, a solvent is usually used. Exemplary solventsinclude ethers such as diethylether, 1,2-dimethoxyethane andtetrahydrofuran; and acid amides such as N,N-dimethylformamide andN-methylpyrrolidone.

The reaction temperature and reaction time in the Step (l) are typicallyabout 0 to 100° C. and 10 minutes to 24 hours, respectively. Thereaction may be followed by a conventional treatment and purification bycolumn chromatography, recrystallization or the like as required torecover the reaction product.

The substituted pyrazole ring of the formula (5) in which D is a halogenatom (X) may be obtained by reacting a halogenating agent on a pyrazolederivative of the following formula (16) (Step (m)). X is a chlorine,bromine or iodine atom.Step (m):

With respect to the amounts of the reagents subjected to the reaction, 1to 10 equivalents of the halogenating agent is used per equivalent ofthe pyrazole derivative of the formula (16).

Exemplary halogenating agents include chlorine gas, N-chlorosuccinimide,1,5-dichloro-5,5-dimethylhydantoin, bromine, N-bromosuccinimide and1,5-dibromo-5,5-dimethylhydantoin.

In the above reaction, a solvent is usually used. The solventsemployable include halogenated solvents such as dichloromethane,chloroform, carbon tetrachloride and 1,2-dichloroethane.

The reaction temperature and reaction time in the Step (m) are typicallyabout 0 to 30° C. and 10 minutes to 24 hours, respectively. The reactionmay be followed by a conventional treatment and purification by columnchromatography, recrystallization or the like as required to prepare theobjective compound.

The haloalkyleneoxime ester derivative represented by the formula (6)may be obtained by reacting a hydroxylamine derivative of the formula(19) with a halopyruvate derivative of the formula (18) (Step (n)).Step (n):

With respect to the amounts of the reagents subjected to the reaction, 1to 3 equivalents, preferably 1 to 1.5 equivalents of the hydroxylamineof the formula (19) is used per equivalent of the halopyruvatederivative of the formula (18).

In the above reaction, a solvent is usually used. The solventsemployable include alcohols such as methanol, ethanol, normal propanol,isopropanol, normal butanol and benzyl alcohol; and aromatichydrocarbons such as benzene, toluene, xylene, chlorobenzene andethylbenzene. Of these, methanol, ethanol, benzene and toluene arepreferable.

The reaction may be followed by a conventional treatment, and theresultant reaction product may be subjected to the next reaction withoutpurification.

The reaction temperature and reaction time in the above step aretypically about 0 to 150° C., preferably 20 to 100° C., and 10 minutesto 24 hours, respectively. The reaction may be followed by aconventional treatment, and the resultant reaction product may besubjected to the next reaction without purification.

The inventive compounds (4) may be obtained according to a similarprocess to the above synthesis step (c). In this synthesis, the carboxylacid derivative of the formula (8) is condensed with a substitutedhydrazine having substituent groups R₁₁ and R₁₂ (i.e., H₂NNR₁₁R₁₂) inplace of the amine R₄—NH—R₅ Reaction conditions are the same as in theStep (c). Some types of the hydrazine derivatives can act on the esterderivative of the formula (7) to directly synthesize the inventivecompound.

Herbicidal Effects

Herbicidal Spectrum (Upland Fields)

Some types of the inventive compounds are useful as upland field andnon-crop land herbicides. They, in any treatment among soil treatment,soil incorporation treatment and foliage treatment, can exert in a smalldose high herbicidal effects on various species of field weeds.Controllable weeds are, for example, broad leaf-weeds, includingSolanaceae weeds such as Solanum nigrum and Datura stramonium, Malvaceaeweeds such as Abutilon theophrasti and Sida spinosa, Convolvulaceaeweeds such as Ipomoea spps. (e.g., Ipomoea purpurea) and Calystegiaspps., Amaranthaceae weeds such as Amaranthus lividus and Amaranthusretroflexus, Compositae weeds such as Xanthium pensylvanicum, Ambrosiaartemisiaefolia, Helianthus annuus, Galinsoga ciliata, Cirsium arvense,Senecio vulgaris and Erigeron annus, Cruciferae weeds such as Rorippaindica, Sinapis arvensis and Capsella Bursapastoris, Polygonaceae weedssuch as Polygonum Blumei and Polygonum convolvulus, Portulacaceae weedssuch as Portulaca oleracea, Chenopodiaceae weeds such as Chenopodiumalbum, Chenopodium ficifolium and Kochia scoparia, Caryophyllaceae weedssuch as Stellaria media, Scrophulariaceae weeds such as Veronicapersica, Commelinaceae weeds such as Commelina communis, Labiatae weedssuch as Lamium amplexicaule and Lamium purpureum, Euphorbiaceae weedssuch as Euphorbia supina and Euphorbia maculata, Rubiaceae weeds such asGalium spurium and Rubia akane, Violaceae weeds such as Violamandshurica, and Leguminosae weeds such as Sesbania exaltata and Cassiaobtusifolia; and other weeds, including Gramineous weeds such as Sorghambicolor, Panicum dichotomiflorum, Sorghum halepense, Echinochloacrus-galli var. crus-galli, Echinochloa crus-galli var. praticola,Echinochloa utilis, Digitaria adscendens, Avenafatua, Eleusine indica,Setaria viridis, Alopecurus aegualis and Poa annua, and Cyperaceousweeds such as Cyperus rotundus (Cyperus esculentus).

Further, the inventive compounds can control widespread weeds such asthose emerging in mowed fields, fallow lands, lands under perennialcrops, pastures, lawns, railway sides, athletic grounds, vacant lots,forests, farm loads, levees and other non-crop lands.

Crop Selectivity (Upland Fields)

Some types of the inventive compounds do not adversely affect vegetationof main crops such as Oryza sativa, Triticum aestivum, Hordeum vulgare,Sorghum bicolor, Arachis hypogaea, Zea mays, Glycine max, Gossypium spp.and Beat vulgaris, lawn grasses such as Zoysia japonica and Zoysiamatrella, and garden crops such as flowers, ornamental plants andvegetable crops including Raphanus sativus and Brassica napus.

Herbicidal Spectrum (Paddy Fields)

Some types of the inventive compounds are useful as paddy fieldherbicides. They, in any treatment of waterlogged soil treatment andfoliage treatment, can exert in a small dose high herbicidal effects onvarious species of paddy weeds. Such weeds are, for example,Alismataceae weeds such as Alisma canaliculatum, Sagittaria trifolia andSagittaria pygmaea, Cyperaceous weeds such as Cyperus difformis, Cyperusserotinus, Scirpus juncoides, Eleocharis kuroguwai and Eleocharisacicularis, Scrophulariaceae weeds such as Lindernia pyxidaria,Pontederiaceae weeds such as Monochoria vaginalis, Potamogetonaceaeweeds such as Potamogeton distihctus, Umbelliferae weeds such asOenanthe javanica, Lythraceae weeds such as Rotala indica and Ammanniamultiflora, Elatinaceae weeds such as Elatine triandra, and Graminaceousweeds such as Echinochloa oryzicola, Echinochloa crus-galli var.formosensis and Echinochloa crus-galli var. crus-galli.

Crop Selectivity (Paddy Rice)

The inventive compounds do not pose a significant chemical hazard totransplantation paddy rice or direct-sowing paddy rice.

Effect on Aquatic Plants

The inventive compounds exhibit an efficacy onalgae such as blue-greenalgae, and aquatic weeds such as Eichhornia crassipes, which emerge increeks, canals, lakes, marshes, ponds and water reservoirs.

Formulations

The herbicide compositions according to the present invention containone or more kinds of the inventive compounds as active ingredients. Inthe formulation of the compositions, the active ingredient(s) is (are)combined with a solid or liquid carrier and optionally with a surfactantand other adjuvant, and the mixture is formulated into conventionalforms of agricultural chemicals, such as wettable powders, powders,granules, pellets, concentrated liquids, aerosols, water-solublepowders, emulsifiable concentrates, suspension concentrates, flowablesand packs. For application in paddy fields in particular, the herbicidecomposition is favorably formulated into granules and packed in awater-soluble polymer film as will be described later.

For the preparation of the herbicide compositions, any processconventionally used in formulation of agricultural chemicals may beemployed. If necessary, the active ingredients for the agriculturalchemicals may be finely pulverized in advance by an air mill or a hummermill, and mixed with a carrier, a surfactant or the like. To produceformulations other than powders, appropriate treatment may be performeddepending on the type of the objective formulation. In the case ofgranule formulations, for example, required ingredients may be mixed,kneaded and granulated to the desired size with an extruder according toa common granulation method for granular agricultural chemicals. For thepreparation of suspension formulations, the active ingredient(s) may bedispersed into water containing a carrier and a surfactant as wettingagent, dispersing agent and suspending agent, and the suspendedparticles may be ground by a wet grinding mill such as DYNO-Mill or sandgrinder and optionally mixed with an adjuvant or the like. Thewater-soluble powders and wettable powders may be dissolved or suspendedin water for application. The emulsifiable concentrates may be preparedby mixing the active ingredient(s) with an appropriate emulsifying agentby a homogenizer, a pressure emulsifier or DYNO-Mill.

Additives

In the practical application of the inventive compounds, the compoundsmay be used as they are. They may also be employed as compositions incombination with useful additives generally used for formulation, suchas carriers, surfactants, solvents, and adjuvants effective forenhancing dispersion and for improving other properties of the activeingredients (e.g., thickening agents, antifreezing agents, anti-foamingagents, antiseptic agents, stabilizing agents and colorants).

Examples of the solid carriers or diluents include fine powders orgranules of plant substances, fibrous materials, synthetic plasticpowders, clays (such as kaolin, bentonite, terra abla, diatomaceousearth and Fubasami clay), talcs, inorganic materials (pumice, powderedsulfur, active carbon and calcium carbonate), and chemical fertilizers(such as ammonium sulfate, ammonium phosphate and urea). Examples of theliquid carriers or diluents include water, alcohols, ketones, ethers,aromatic hydrocarbons, aliphatic hydrocarbons, esters, nitrites, amides(N,N-dimethylformamide, dimethyl sulfoxide), and halogenatedhydrocarbons.

Examples of the surfactants include alkylsulfuric acid esters, alkylsulfonates, alkylarylsulfonic acids, alkylaryl. ethers, polyethyleneglycol ethers, polyhydric alcohol esters and sugar alcohol derivatives.

Examples of the spreading or dispersing agents include casein, gelatin,starch powders, carboxymethylcellulose, gum arabic, alginic acid,lignin, bentonite, polyvinylalcohol, pineapple oil, molasses and agarand the like.

Examples of the stabilizers include isopropylphosphate mixtures,tricresyl phosphate, tall oil, epoxy oil, surface-active agents, fattyacids and esters thereof. As will be described later, the formulationsaccording to the present invention may contain other fungicides,insecticides, herbicides or fertilizers in addition to the aboveingredients.

Active Ingredient Concentrations

The concentrations of the active ingredients in the herbicidecompositions of the invention can be variously changed depending on theformulation forms as described above. In the case of the wettablepowders, the active ingredient concentration is in the range of 5 to90%, and preferably about 10 to 85%. For the emulsifiable concentrates,the active ingredient concentration is in the range. of 3 to 70%, andpreferably about 5 to 60%. For the granules, the active ingredientconcentration is in the range of 0.01 to 50%, and preferably about 0.05to 40%.

Usage (Dosage and Application Method)

Wettable powders or emulsifiable concentrates thus formulated may besprayed or incorporated as suspensions or emulsions diluted with waterto a given concentration, before or after sprouting of the target weeds.Granule formulations can be directly applied or incorporated as suchbefore or after sprouting of the target weeds. In practical applicationof the herbicide composition of the invention as a herbicide, it will beappropriately used in such an amount that gives not less than 0.1 g ofthe active ingredient(s) per hectare.

When the inventive compound is used as an active ingredient of aherbicide, the amount thereof is usually in the range of 10 g to 8000 g,preferably 10 g to 2000 g per hectare, although it varies withmeteorological conditions, formulation forms, application times,application methods, soil conditions, crops in cultivation, targetweeds, etc. In the case of emulsifiable concentrates, wettable powders,suspension concentrates, concentrated emulsions, water-dispersiblegranules, liquid formulations and the like, given amounts of suchformulations are applied after usually diluted with 10 to 1000 liters ofwater (optionally containing adjuvants such as a spreader) per hectare.On the other hand, granules and some types of suspension concentratesand liquid formulations are generally applied without any dilution.Examples of the adjuvants include the surfactants described above,polyoxyethylene fatty acids (esters), ligninsulfonates, abietates,dinaphthylmethanedisulfonate, and vegetable oils such as crop oilconcentrate, soybean oil, corn oil, cotton seed oil and sunflower oil.

Combination Use

The herbicide compositions of the invention may be used as mixtures withone or more plant protecting agents, such as fungicides, insecticides,herbicides, nematicides, acaricides, bactericides, plant growthregulators, fertilizers and soil improvers.

The inventive compounds may be used in combination with a compound(s)that shows growth controlling or regulating activities on valuableplants such as crops, ornamental plants and fruit trees. Such plantgrowth controlling compounds include, but not limited to, ethephon,indoleacetic acid, ethychlozate, cloxyfonac, dichlorprop,1-naphthylacetamide, 4-CAP, benzylaminopurine, forchlorfenuron,gibberellin, maleic hydrazide, inabenfide, uniconazole-P, chlormequat,paclobutrazole, flurprimidol, mepiquat chloride, prohexadione calcium,trinexapac ethyl, daminozide, mefluidide, isoprothiolane and oxinesulfate. These may be used singly or as a mixture of two or more kinds.

Examples of the fungicides include, but not limited to, phthalide,flutolanil, mepronil, S-658, pyroquilon, tricyclazole, probenazole,isoprothio-lane, iprobenfos, tecloftalam and benomyl. Examples of theinsecticides include, but not limited to, isoxathion, trichlorophon,propaphos, diazinon, formothion, disulfoton, dimethoate, monocrotophos,acephate, carbofuran, carbosulfan, thiocyclam, cartap, bensultap,benfuracarb, furathibcarb, carbaryl, buprofezin, fenobucarb, metolcarb,propoxur, methomyl, imidacloprid, nitenpyram, cycloprothrin, ethofenproxand silafluofen. These may be used singly or as a mixture of two or morekinds.

Herbicide Mixture

Usage of the herbicide composition as mixed further with otherherbicidal component brings about reduction in application dose andlabor saving for application. Owing to synergy effects of such mixedherbicides, wider herbicidal spectrum and higher herbicidal performancecan be expected in the herbicide composition as described herein. Theherbicide composition may be mixed with two or more known herbicides.Such herbicides include atrazine, cyanazine, dimethametryn, metribuzin,prometryn, simazine, simetryn, chlortoluron, diuron, daimuron,fluometuron, isoproturon, linuron, methabenzthiazuron, amicarbazone,bromoxynil, ioxynil, ethalfluralin, pendimethalin, trifluralin,acifluorfen, acifluorfen-sodium, bifenox, chlomethoxynil, fomesafen,lactofen, oxadiazon, oxadiargyl, oxyfluorfen, carfentrazone-ethyl,flumiclorac-pentyl, flumioxazine, fluthiacet-methyl, sulfentrazone,thidiazimin, azafenidin, pyraflufen-ethyl, cinidon-ethyl, difenzoquat,diquat, paraquat, 2,4-D, 2,4-DB, DCPA, MCPA, MCPB, clomeprop,clopyralid, dicamba, dithiopyr, fluroxypyr, mecoprop, naploanilide,phenothiol, quinclorac, triclopyr, thiazopyr, acetochlor, alachlor,butachlor, diethatyl-ethyl, metolachlor, pretilachlor, propachlor,bensulfuron-methyl, chlorsulfuron, chlorimuron-ethyl,halosulfuron-methyl, metsulfuron-methyl, nicosulfuron,primisulfuron-methyl, pyrazosulfuron-ethyl, sulfometuron-ethyl,thifensulfuron-methyl, triasulfuron, tribenuron-methyl, oxasulfuron,azimsulfuron, cloransulam-methyl, cyclosulfamuron, flumetsulam,florasulam, flupyrsulfuron, flazasulfuron, imazosulfuron, metosulam,diclosulam, prosulfuron, rimsulfuron, triflusulfuron-methyl,ethoxysulfuron, sulfosulfuron, flucarbazone-sodium, procarbazone-sodium(MKH-6561), imazamethabenz-methyl, imazapyr, imazaquin, imazethapyr,imazameth, imazamox, bispyribac-sodium, pyriminobac-methyl,pyrithiobac-sodium, alloxydim-sodium, clethodim, sethoxydim,tralkoxydim, tepraloxydim, profoxydim (BAS-625H), diclofop-methyl,fenoxaprop-ethyl, fenoxaprop-p-ethyl, fluazifop-buthyl,fluazifop-p-butyl, haloxyfop-methyl, quizalofop-p-ethyl,cyhalofop-butyl, clodinafop-propargyl, benzofenap, clomazone,diflufenican, norflurazone, pyrazolate, pyrazoxyfen, picolinafen,beflubutamid, flurtamone, isoxaflutole, sulcotrione, benzobicyclon,mesotrione, glufosinate-ammonium, glyphosate, bentazone, benthiocarb,bromobutide, butamifos, butylate, dimepiperate, dimethenamid, DSMA,EPTC, esprocarb, isoxaben, mefenacet, molinate, MSMA, piperophos,pyributicarb, prosulfocarb, propanil, pyridate, triallate, cafenstrol,flupoxam, flufenacet, diflufenzopyr, triaziflam, pentoxazone, indanofan,metobenzuron, oxaziclomefone and fentrazamide.

These compounds are described in a catalog of Farm Chemical Handbook(Meister Publishing Company) (1997), SHIBUYA INDEX (8th edition) (1999),The Pesticide Manual (British crop protection council) 12th edition(2000), and Herbicide research conspectus (Hakuyu-sha). The above listedcompounds are just illustrative and not exclusive. The compounds may beused singly or as a mixture of two or more kinds.

The appropriate mixing ratio between the inventive compound and otherherbicide(s) may vary depending on the type of active ingredients of theadditional herbicide (s). However, it is generally in the range of1:0.01 to 1:10, by weight. When the herbicide compositions of theinvention are used with the aforesaid other herbicide(s), theformulation process is not specifically restricted. For example, theinventive compound and other active ingredient(s) such as the aforesaidadditional herbicide(s) are each previously mixed with a solid carrier,a liquid carrier, a surfactant or other adjuvant to give emulsifiableconcentrates, wettable powders, suspension concentrates, water-solublegranules, water-soluble powders, aqueous solutions, water-dispersiblegranules or the like, followed by mixing together. It is also possiblethat the inventive compound is premixed with the additional herbicide(s)and thereafter the admixture is mixed with a solid carrier, a liquidcarrier, a surfactant or other formulation adjuvant to yield anemulsifiable concentrate, wettable powder, a suspension concentrate,granules, a concentrated emulsion, water-dispersible granules or thelike. The resulting formulations will contain the inventive compound andother herbicides as active ingredients in a total amount of 0.5 to 80%by weight, preferably 1.5 to 70% by weight.

Application Method

The formulated compositions of the present invention may be applied toplants to be controlled directly or after diluted with water or thelike. The application may be performed according to a variety ofmethods. Exemplary application techniques are spraying or spreading,application of creamlike- or paste-formulated herbicides, vaporapplication, and application of slow release granular herbicides.

The herbicide compositions of the invention can treat plants by beingdirectly sprayed, spread or applied onto the targets, or by being spreadover or incorporated in the soil around the plants, paddy field, etc. Inthe case of paddy fields, any application methods may be employed, suchas carrying the herbicide composition with the flow of agriculturalwater from a water intake, dropping the composition from a levee intothe paddy field and allowing it to spread, or setting the composition toa transplanting machine of rice seedlings in a manner adapted for theherbicide application.

When the herbicide composition is to be applied on a water surface, anembodiment of the invention where the herbicide composition is filledand packed in a water-soluble or water-degradable bag is preferable fromthe viewpoint of handling and application. When such floatable packs aredispersed on a waterlogged field, they favorably float on the watersurface and spread (diffuse) away. Consequently, the active ingredientsof the herbicide can be uniformly dispersed over or into the paddyfield. Therefore, reduction can be achieved in labor of herbicideapplication and phytotoxicity, and stable effects can be expected.

In order that the herbicide composition become capable of floating onthe water surface, it is required that either the specific gravity ofthe composition is regulated to less than 1.0, preferably 0.95 or less,or the composition contains a foaming agent such as a carbonate and awater-soluble solid acid.

In application of the herbicide formulation of the invention in whichthe herbicide composition is packed in a water-soluble orwater-degradable bag, the desired aim can be accomplished only bydropping the formulation directly in a waterlogged field in a ratio of 3to 20 packs per 10a. Dropped in water, these packs will diffuse afloaton the water surface, otherwise submerge once but soon resurface anddiffuse afloat on the water surface, or diffuse while repeatedlysubmerging and soon resurfacing, i.e., they submerge but soon resurfaceand diffuse afloat on the water surface again and again. Generally,floatable herbicide formulations of such a type that they submerge andthen resurface are capable of quick resurfacing and unlikely to becomecaptured on the soil surface. As described above, the formulations ofthe present invention have excellent spreadability (diffusionproperties) and diffuse evenly over the paddy field. These attributesallow the applicator to achieve uniform dispersion of the formulationseven without stepping into the paddy field, and labor can be reduced.Accordingly, the above floatable formulations of the herbicidecomposition are a preferred embodiment of the present invention.

EXAMPLES

The present invention is further described with reference to thefollowing examples and test examples, but it should be construed thatthe invention is in no way limited to those examples.

In the following description, the term “part(s)” means “part(s) byweight”.

Synthesis of Pyrazole Derivatives

Hereinbelow, synthesis of the inventive compounds represented by theformula (1) or (4) will be illustrated in detail by examples.

Production Example 1 Synthesis of ethyl 2-methoxyimino-3-bromopropionate(represented by the formula (6) in the Step (n) in which n is 0, R₁ andR₂ are both hydrogen atoms, Z is a bromine atom, R₃ is a methoxy groupand R₁₃ is ethyl)

Ethyl bromopyruvate (80% purity), 38.9 g (200 mmol as calculated on anassumption of 100% purity) was dissolved in 100 ml of ethanol. At roomtemperature, 16.6 g (200 mmol) of methoxyamine hydrochloride was addedto the solution, followed by heating under reflux for 2 hours. Afterreaction had been completed, ethanol was distilled away, and 200 ml ofethyl acetate was added to the residue. The reaction product was washedsequentially with a saturated aqueous solution of sodiumhydrogencarbonate and an aqueous solution of sodium chloride, and thendried over anhydrous magnesium sulfate. Filtration and subsequentdistillation to remove the solvent gave 36.9 g (165 mmol) of ethyl2-methoxyimino-3-bromopropionate as a light yellow oily matter. Theyield was 80%. The product synthesized was subjected to the nextreaction without purification.

Production Example 2 Synthesis of2-methoxyimino-3-((4′-methoxyphenyl)-4-methyl-pyrazole)-1-yl-propanoicacid-N-methylamide (Compound No. 41 represented by the formula (1) inwhich n is 0, A is 4-methoxyphenyl, D is methyl, E is a hydrogen atom,R₁ and R₂ are both hydrogen atoms, R₃ is methyl, R₄ is a hydrogen atomand R₅ is methyl)

(Step 1)

10 g (60.9 mmol) of 4′-methoxypropiophenone was dissolved in 100 ml ofmethyl formate. At room temperature, sodium methoxide, 15.3 g (79.2mmol) at a concentration of 28% in methanol solution was dropwise addedto the solution over a period of 30 minutes, followed by stirring at thesame temperature for 6 hours. To the reaction mixture was added 100 mlof water, and the solution pH was adjusted to 1 with concentratedhydrochloric acid, followed by stirring for further 1 hour. Thereafter,the reaction mixture was extracted with 100 ml of ethyl acetate threetimes. The organic phase was washed with a saturated aqueous solution ofsodium chloride and then dried over anhydrous magnesium sulfate.Filtration and subsequent distillation to remove the solvent gave 9.8 g(51.0 mmol) of 2-formyl-4′-methoxypropiophenone as a light yellowcrystal. The yield was 84%. The product synthesized was subjected to thenext reaction without purification.

(Step 2)

9.8 g (51.0 mmol) of the 2-formyl-4′-methoxypropiophenone synthesized inStep 1 was dissolved in 150 ml of ethanol. At room temperature, 3.8 g(61.2 mmol) of 80% hydrazine hydrate was dropwise added to the solution,followed by stirring at the same temperature for 1 hour and further byheating under reflux for 2 hours. After reaction had been completed, thereaction mixture was cooled to room temperature and the solvent wasdistilled away. As a result, 8.4 g (44.9 mmol) of3-(4′-methoxyphenyl)-4-methylpyrazole was obtained as an orange oilymatter. The yield was 88%. The product synthesized was subjected to thenext reaction without purification.

(Step 3)

1.6 g (8.5 mmol) of the 3-(4′-methoxyphenyl)-4-methylpyrazolesynthesized in Step 2 was dissolved in 30 ml of N,N-dimethylformamide.At room temperature, 1.4 g (10.2 mmol) of potassium carbonate and 2.9 g(10.2 mmol) of the ethyl 2-methoxyimino-3-bromopropionate synthesized inProduction Example 1 were sequentially added to the solution, followedby heating at 110° C. under stirring for 4 hours. After reaction hadbeen completed, the reaction mixture was poured into 100 ml of water,and was extracted with 50 ml of diethylether three times. Theorganic-phase was washed with a saturated aqueous solution of sodiumchloride and then dried over anhydrous magnesium sulfate. Filtration andsubsequent distillation to remove the solvent gave 2.6 g (7.4 mmol) ofethyl2-methoxyimino-3-((4′-methoxyphenyl)-4-methyl-pyrazole)-1-yl-propanoatein a 100 ml three-necked flask. The yield was 87%. The productsynthesized was subjected to the next reaction without purification.

(Step 4)

1.1 g (3.1 mmol) of the ethyl2-methoxyimino-3-((4′-methoxyphenyl)-4-methyl-pyrazole)-1-yl-propanoatesynthesized in Step 3 was combined with a methanol solution of 40%methylamine, followed by stirring at room temperature for 4 hours. Afterreaction had been completed, the solvent was distilled away. Theresultant residue was purified by silica gel column chromatography usingchloroform as an eluting solution. Subsequently, the solvent was removedby distillation to yield 0.96 g (2.9 mmol) of2-methoxyimino-3-((4′-methoxyphenyl)-4-methyl-pyrazole)-1-yl-propanoicacid-N-methylamide as a white crystal. The yield was 94%.

Production Example 3 Synthesis of2-methoxyimino-3-((2′,6′-difluorophenyl)-4-methyl-pyrazole)-1-yl-propanoicacid-N-methylamide (Compound No. 58 represented by the formula (1) inwhich n is 0, A is 2, 6-difluorophenyl, D is methyl, E is a hydrogenatom, R₁ and R₂ are both hydrogen atoms, R₃ is methyl, R₄ is a hydrogenatom and R₅ is methyl)

(Step 1)

4.9 g (29.0 mmol) of 2,6-difluoropropiophenone was dissolved in 100 mlof toluene. To the solution, 6.9 g (58.0 mmol) of N,N-dimethylformamidedimethylacetal was added, followed by heating under reflux for 8 hoursand further by stirring at the same temperature for 6 hours. Afterreaction had been completed, the toluene and excess ofN,.N-dimethylformamide dimethylacetal were distilled away to yield 6.2 g(27.5 mmol) of1-(2′,6′-difluorophenyl)-2-methyl-3-N,N-dimethylamino-2-propene as anorange resinous substance. The yield was 95%.

(Step 2)

6.2 g (27.5 mmol) of the1-(2′,6′-difluorophenyl)-2-methyl-3-N,N-dimethylamino-2-propenesynthesized in Step 1 was dissolved in 150 ml of ethanol. At roomtemperature, 2.4 g (37.7 mmol) of 80% hydrazine hydrate was dropwiseadded to the solution, followed by stirring at the same temperature for1 hour and further by heating under reflux for 2 hours. After reactionhad been completed, the reaction mixture was cooled to room temperatureand the solvent was distilled away. As a result, 4.8 g (24.7 mmol) of3-(2′,6′-difluorophenyl)-4-methylpyrazole was obtained as an orange oilymatter. The yield was 85%. The product synthesized was subjected to thenext reaction without purification.

(Step 3)

2.0 g (10.0 mmol) of the 3-(2′,6′-difluorophenyl)-4-methylpyrazolesynthesized in Step 2 was dissolved in 40 ml of N,N-dimethylformamide.At room temperature, 1.7 g (12.0 mmol) of potassium carbonate and 3.5 g(12.4 mmol) of the ethyl 2-methoxyimino-3-bromopropionate synthesized inProduction Example 1 were sequentially added to the solution, followedby heating at 110° C. under stirring for 4 hours. After reaction hadbeen completed, the reaction mixture was poured into 100 ml of water,and was extracted with 50 ml of diethylether three times. The organicphase was washed with a saturated aqueous solution of sodium chlorideand then dried over anhydrous magnesium sulfate. Filtration andsubsequent distillation to remove the solvent gave 2.6 g (7.7 mmol) ofethyl2-methoxyimino-3-((2′,6′-difluorophenyl)-4-methyl-pyrazole)-1-yl-propanoate.The yield was 62%. The product synthesized was subjected to the nextreaction without purification.

(Step 4)

2.6 g (7.7 mmol) of the ethyl2-methoxyimino-3-((2′,6′-difluorophenyl)-4-methyl-pyrazole)-1-yl-propanoatesynthesized in Step 3 was combined with 30 ml of a methanol solution of40% methylamine, followed by stirring at room temperature for 4 hours.After reaction had been completed, the solvent was distilled away. Theresidue was purified by silica gel column chromatography usingchloroform as an eluting solution. Subsequently, the solvent was removedby distillation to yield 2.0 g (6.2 mmol) of2-methoxyimino-3-((2′,6′-difluorophenyl)-4-methyl-pyrazole)-1-yl-propanoicacid-N-methylamide as a white crystal. The yield was 81%.

Production Example 4 Synthesis of3-(phenyl-4-methyl-pyrazole)-1-yl-propanoic acid-N-cyclopropylamide(Compound No. 21 represented by the formula (1) in which n is 0, A isphenyl, D is methyl, E is a hydrogen atom, R₁ and R₂ are both hydrogenatoms, R₃ is methyl, R₄ is a hydrogen atom and R₅ is cyclopropyl)

(Step 1)

5.0 g (37.3 mmol) of propiophenone was dissolved in 100 ml of methylformate. At room temperature, 8.6 g (44.7 mmol) of a methanol solutionof 28% sodium methoxide was dropwise added to the solution over a periodof 30 minutes, followed by stirring at the same temperature for 6 hours.To the reaction mixture was added 100 ml of water, and the solution pHwas adjusted to 1 with concentrated hydrochloric acid, followed bystirring for further 1 hour. Thereafter, the reaction mixture wasextracted with 100 ml of ethyl acetate three times. The organic phasewas washed with a saturated aqueous solution of sodium hydrochloride andthen dried over anhydrous magnesium sulfate. Filtration and subsequentdistillation to remove the solvent gave 5.7 g (35.4 mmol) of2-formylpropiophenone as a light yellow crystal. The yield was 95%. Theproduct synthesized was subjected to the next reaction withoutpurification.

(Step 2)

5.7 g (35.4 mmol) of the 2-formylpropiophenbne synthesized in Step 1 wasdissolved in 150 ml of ethanol. At room temperature, 2.4 g (37.7 mmol)of 80% hydrazine hydrate was dropwise added to the solution, followed bystirring at the same temperature for 1 hour and further by heating underreflux for 2 hours. After reaction had been completed, the reactionmixture was cooled to room temperature and the solvent was distilledaway. As a result, 5.2 g (33.2 mmol) of 3-phenyl-4-methylpyrazole wasobtained as a white crystal. The yield was 88%. The product synthesizedwas subjected to the next reaction without purification.

(Step 3)

2.0 g (12.7 mmol) of the 3-phenyl-4-methylpyrazole synthesized in Step 2was dissolved in 40 ml of N,N-dimethylformamide. At room temperature,2.1g (15.2 mmol) of potassium carbonate and 3.4 g (15.2 mmol) of theethyl 2-methoxyimino-3-bromopropionate synthesized in Production Example1 were sequentially added to the solution, followed by heating at 110°C. under stirring for 4 hours. After reaction had been completed, thereaction mixture was poured into 100 ml of water, and was extracted with50 ml of diethylether three times. The organic phase was washed with asaturated aqueous solution of sodium hydrochloride and then dried overanhydrous magnesium sulfate. Filtration and subsequent distillation toremove the solvent gave 2.9 g (9.6 mmol) of ethyl2-methoxyimino-3-(phenyl-4-methyl-pyrazole)-1-yl-propanoate. The yieldwas 63%. The product synthesized was subjected to the next reactionwithout purification.

(Step 4)

2.9 g (9.6 mmol) of the ethyl2-methoxyimino-(3-phenyl-4-methyl-pyrazole)-1-yl-propanoate synthesizedin. Step 3 was dissolved in a mixed solvent consisting of 20 ml ofethanol and 20 ml of water. At room temperature, 0.5 g (9.6 mmol) ofpotassium hydroxide powder (85%) was added to the solution, followed bystirring at the same temperature for 1 hour. After reaction had beencompleted, the pH of the reaction mixture was adjusted to 1 withconcentrated hydrochloric acid. Thereafter, the reaction mixture wasextracted with 50 ml of ethyl acetate three times. The organic phase waswashed with a saturated aqueous solution of sodium hydrochloride andthen dried over anhydrous magnesium sulfate. Filtration and subsequentdistillation to remove the solvent gave 2.6 g (9.5 mmol) of2-methoxyimino-3-(phenyl-4-methylpyrazole)-1-yl-propanoic acid. Theyield was 99%. The product synthesized was subjected to the nextreaction without purification.

(Step 5)

2.1 g (7.7 mmol) of the2-methoxyimino-3-(phenyl-4-methylpyrazole)-1-yl-propanoic acidsynthesized in Step 4 was dissolved in 30 ml of tetrahydrofuran. At roomtemperature, 1.9 g (11.5 mmol) of carbonyldiimidazole was added to thesolution, followed by stirring at the same temperature for 30 minutes.Subsequently, 1.3 g (23.1 mmol) of cyclopropylamine was added, and themixture was stirred at the same temperature for 2 hours. After reactionhad been completed, the reaction mixture was poured into 50 ml of water,and was extracted with 50 ml of diethylether three times. The organicphase was dried over anhydrous magnesium sulfate, followed by filtrationand distillation to remove the solvent. The residue was purified bysilica gel column chromatography using chloroform as an elutingsolution. Subsequently, the solvent was removed by distillation to yield1.0 g (3.2 mmol) of 3-(phenyl-4-methyl-pyrazole)-1-yl-propanoicacid-N-cyclopropylamide as a white crystal. The yield was 42%.

Compounds Nos. 1-20, 22-40, 42-57 and 59-124 listed in Table 1 werefurther prepared in addition to the compounds Nos. 41 (ProductionExample 2), 58 (Production Example 3) and 21 (Production Example 4).They were synthesized by the procedures illustrated in ProductionExamples 1 to 4, except that the starting materials were altered tocompounds having corresponding groups to those in the objectivecompounds. NMR spectrum data and physical properties of these compoundsare shown in Tables 2 and 3 respectively.

In Table 1, Ph, Me, Et, Bn, Pr, Bu, Pen, Hex, 1, c and t denote phenyl,methyl, ethyl, benzyl, propyl, butyl, pentyl, hexyl, linear, cyclic andtertiary respectively. TABLE 1 No. A D E R1 R2 R3 R4 R5 n 1 H Me H H HMe H Me 0 2 Me Me H H H Me H Me 0 3 Et Me H H H Me H Me 0 4 n-Pr Me H HH Me H Me 0 5 i-Pr Me H H H Me H Me 0 6 c-Pr Me H H H Me H Me 0 7 n-BuMe H H H Me H Me 0 8 t-Bu Me H H H Me H Me 0 9 c-Bu Me H H H Me H Me 010 c-Pen Me H H H Me H Me 0 11 c-hex Me H H H Me H Me 0 12 CF₃ Me H H HMe H Me 0 13 Ph H H H H Me H Me 0 14 Ph Cl H H H Me H Me 0 15 4-F—Phethynyl H H H Me H Me 0 16 Ph Me H H H Me H H 0 17 4-Cl—Ph Me H H H Me HH 0 18 Ph Me H H H Me H Me 0 19 Ph Me H H H Me H Et 0 20 Ph Me H H H MeH I—Pr 0 21 Ph Me H H H Me H c-Pr 0 22 Ph Me H H H Me H t-Bu 0 23 Ph MeH H H Me H c-Pen 0 24 Ph Me H H H Me H c-Hex 0 25 Ph Me H H H Me H2-Me-c-Hex 0 26 Ph Me H H H Me H 2-Propenyl 0 27 Ph Me H H H Me H2-Propynyl 0 28 Ph Me H H H Me H 2,2-(OEt)₂-Ethyl 0 29 Ph Me H H H Me HPh 0 30 Ph Me H H H Me H Bn 0 31 Ph Me H H H Me H α-Fenethyl 0 32 Ph MeH H H Me H 3′,4′-(OMe)₂-β-Fenethyl 0 33 Ph Me H H H Me H CH₂CN 0 34 PhMe H H H Me H CH₂CF₃ 0 35 2-Me—Ph Me H H H Me H Me 0 36 3-Me—Ph Me H H HMe H Me 0 37 4-Me—Ph Me H H H Me H Me 0 38 4-i-Pr—Ph Me H H H Me H Me 039 4-Ph—Ph Me H H H Me H Me 0 40 4-CF₃—Ph Me H H H Me H Me 0 41 4-OMe—PhMe H H H Me H Me 0 42 2-F—Ph Me H H H Me H Me 0 43 3-F—Ph Me H H H Me HMe 0 44 4-F—Ph Me H H H Me H Me 0 45 2-Cl—Ph Me H H H Me H Me 0 463-Cl—Ph Me H H H Me H Me 0 47 4-Cl—Ph Me H H H Me H Me 0 48 2-Br—Ph Me HH H Me H Me 0 49 3-Br—Ph Me H H H Me H Me 0 50 4-Br—Ph Me H H H Me H Me0 51 4-CN—Ph Me H H H Me H Me 0 52 3-PhO—Ph Me H H H Me H Me 0 534-PhO—Ph Me H H H Me H Me 0 54 4-BnO—Ph Me H H H Me H Me 0 55 2,3-F₂—PhMe H H H Me H Me 0 56 2,4-F₂—Ph Me H H H Me H Me 0 57 2,5-F₂—Ph Me H H HMe H Me 0 58 2,6-F₂—Ph Me H H H Me H Me 0 59 3,4-F₂—Ph Me H H H Me H Me0 60 3,5-F₂—Ph Me H H H Me H Me 0 61 4-OH—Ph Me H H H Me H Me 0 624-AcO—Ph Me H H H Me H Me 0 63 (Me)₂N(CO)O—Ph Me H H H Me H Me 0 64(Me)₂NSO₂—O—Ph Me H H H Me H Me 0 65 4-CF₂HO—Ph Me H H H Me H Me 0 664-CF₃O—Ph Me H H H Me H Me 0 67 4-FCH₂CF₂O—Ph Me H H H Me H Me 0 684-SMe—Ph Me H H H Me H Me 0 69 4-SO₂Me—Ph Me H H H Me H Me 0 704-SCF₃—Ph Me H H H Me H Me 0 71 3,4-(Me)₂—Ph Me H H H Me H Me 0 722,3-(OMe)₂—Ph Me H H H Me H Me 0 73 2,5-(Cl)₂—Ph Me H H H Me H Me 0 743-F,4-Me—Ph Me H H H Me H Me 0 75 4-F,3-Me—Ph Me H H H Me H Me 0 763-F,4-OMe—Ph Me H H H Me H Me 0 77 4-F,3-OMe—Ph Me H H H Me H Me 0 782-Cl,4-OMe—Ph Me H H H Me H Me 0 79 3-Cl,4-OMe—Ph Me H H H Me H Me 0 803-F,4-Cl—Ph Me H H H Me H Me 0 81 2-F,4-Cl—Ph Me H H H Me H Me 0 824-F,2-Cl—Ph Me H H H Me H Me 0 83 4-F,3-Br—Ph Me H H H Me H Me 0 842-F,3-CF₃—Ph Me H H H Me H Me 0 85 2-F,4-CF₃—Ph Me H H H Me H Me 0 862-F,5-CF₃—Ph Me H H H Me H Me 0 87 3-F,4-CF₃—Ph Me H H H Me H Me 0 883-F,5-CF₃—Ph Me H H H Me H Me 0 89 4-F,2-CF₃—Ph Me H H H Me H Me 0 904-F,3-CF₃—Ph Me H H H Me H Me 0 91 2-CHF₂O,4-OMe—Ph Me H H H Me H Me 092 3,5-F2,4-OMe—Ph Me H H H Me H Me 0 93 Ph Me H H H Me Me Me 0 94 Ph MeH H H Me Et Et 0 95 Ph CO₂Et H H H Me H Me 0 96 Ph SO₂Me H H H Me H Me 097 Ph OMe H H H Me H Me 0 98 Ph Et H H H Me H Me 0 99 Ph Ph H H H Me HMe 0 100 Ph CF₃ H H H Me H Me 0 101 Ph H Ph H H Me H Me 0 102 4-F—Ph MeH H H H H Me 0 103 Ph Me H H H FCH₂ H Me 0 104 4-F—Ph Me H H H FCH₃ H Me0 105 Ph Me H H H 2-propenyl H Me 0 106 Ph Me H H H Bn H Me 0 107 Ph MeH H H 2-propynyl H Me 0 108 Me Ph H H H Me H Me 0 109 Ph Me H H H Me HMe 1 110 4-J1—Ph Me H H H Me H Me 0 111 4-J2—Ph Me H H H Me H Me 0 1124-J3—Ph Me H H H Me H Me 0 113 Ph Me Me H H Me H Me 0 114 Ph Me Me Me HMe H Me 0 115 Ph Me Cl H H Me H Me 0 116 Ph Me Br H H Me H Me 0 117 PhMe I H H Me H Me 0In the formula (2): R6 = R7 = H:J1 R6 = H, R7 = Me:J2In the formula (3): R8 = H, R9 = R10 = Me:J3

TABLE 1-2 Cyclic amines No A D E R1,R2 R3 R4-R5 n 118 Ph Me H H Me G1 0119 Ph Me H H Me G2 0 120 Ph Me H H Me G3 0 121 Ph Me H H Me G4 0 122 PhMe H H Me G5 0

TABLE 1-3 No A D E R1 R2 R3 R11 R12 n 123 Ph Me H H H Me H CO₂Me 0 124Ph Me H H H Me Me Me 0

TABLE 2-1 δ value (ppm, solvent: CDCl3, internal reference:tetramethylsilane 1 2.03(3H, s), 2.89(3H, d), 4.01(3H, s), 5.17(2H, s),6.62(1H, bs), 7.22(1H, s) 11 1.00-2.20(1H, m), 1.99(3H, s), 2.89(3H, d),4.00(3H, s), 5.03(2H, s), 6.97(1H, bs), 7.18(1H, s) 13 2.89(3H, d),4.02(3H, s), 5.27(2H, s), 6.49(1H, d), 7.24-7.82(5H, m) 14 2.87(3H, d),4.01(3H, s), 5.20(2H, s), 6.70(1H, bs), 7.22-7.91(6H, m) 15 2.88(3H, d),3.14(1H, s), 4.05(3H, s), 5.20(2H, s), 6.67(1H, bs), 7.07(2H, t),7.73(1H, s), 8.03(2H, dd) 16 2.20(3H, s), 4.07(3H, s), 5.18(2H, s),5.43(1H, bs), 6.67(1H, bs), 7.20-7.73(6H, m) 17 2.17(3H, s), 4.07(3H,s), 5.17(2H, s), 6.60(2H, bs), 7.25-7.64(5H, m) 18 2.21(3H, s), 2.84(3H,d,), 5.18(2H, s), 6.74(1H, bs), 7.24-7.66(6H, m) 19 1.15(3H, t),2.19(3H, s), 3.35(2H, q), 4.06(3H, s), 5.17(2H, s), 6.72(1H, bs),7.27-7.65(6H, m) 20 2.27(3H, s), 2.58(6H, s), 4.00(3H, s), 5.17(2H, s),7.21-7.70(7H, m) 21 0.61-0.89(4H, m), 2.14(3H, s), 2.62-2.85(1H, m),4.02(3H, s), 5.19(2H, s), 6.89(1H, s), 7.38-7.69(6H, m) 22 1.38(9H, s),2.10(3H, s), 4.04(2H, s), 5.16(2H, s), 6.57(1H, bs), 7.25-7.65(6H, m) 231.21-2.06(8H, m), 2.18(3H, s), 3.86-4.29(1H, m), 4.02(3H, s), 5.17(2H,s), 6.65(1H, bs), 7.21-7.58(6H, m) 24 1.16-1.94(10H, m), 2.18(3H, s),3.65-4.08(1H, m), 4.04(3H, s), 5.17(2H, s), 6.52(1H, bs), 7.25-7.67(6H,m) 25 0.84-2.03(13H, m), 2.20(3H, s), 4.02(3H, s), 5.20(2H, s), 6.49(1H,bs), 7.21-7.70(7H, m) 26 2.19(3H, s), 4.03(3H, s), 5.20(2H, s),5.06-5.30(4H, m), 5.63-6.07(1H, m), 6.82(1H, m)7.22-7.70(6H, m) 272.19(3H, s), 2.21(1H, s), 4.08(3H, s), 4.17(2H, d), 5.18(2H, s),6.99(1H, bs), 7.23-7.72(6H, m) 28 2.10(3H, s), 3.35-4.19(4H, m),4.51(1H, t), 5.20(2H, s), 6.90(1H, bs), 7.25-7.70(7H, m) 29 2.28(3H, s),4.21(3H, s), 4.51, 5.30(2H, s), 7.00-7.85(11H, m), 8.21(1H, bs) 302.20(3H, s), 4.00(3H, s), 4.50(2H, d), 5.21(2H, s), 6.95-7.70(12H, m) 311.50(3H, d), 2.19(3H, s), 4.01(3H, s), 5.19(2H, s), 7.01(1H, d),7.34-7.71(12H, m) 32 2.18(3H, s), 2.69(2H, t), 3.53(2H, q), 3.82(6H, s),4.00(3H, s)5.18(2H, s), 6.68-7.70(10H, m) 33 2.14(3H, s), 4.00(3H, s),4.79(2H, s), 5.17(2H, s), 6.98(1H, bs), 7.25-7.70(5H, m) 34 2.19(3H, s),3.78-4.14(2H, m), 4.09(3H, s), 5.20(2H, s), 7.07(1H, bs), 7.24-7.65(6H,m) 35 1.93(3H, s), 2.22(3H, s), 2.87(3H, d), 4.00(3H, s), 5.20(2H, s),6.70(1H, bs), 7.10-7.25(4H, m), 7.37(1H, s) 36 2.18(3H, s), 2.37(3H, s),2.87(3H, d), 4.03(3H, s), 5.20(2H, s), 6.75(1H, bs), 7.00-7.53(5H, m) 372.14(3H, s), 2.38(3H, s), 2.90(3H, d), 4.05(3H, s), 5.19(2H, s),6.78(1H, bs), 7.14-7.78(5H, m) 38 1.28(6H, s), 2.00(1H, m), 2.00(3H, s),2.90(3H, d), 4.01(3H, s), 5.19(2H, s), 6.56-7.80(6H, m) 39 2.21(3H, s),2.86(3H, d), 4.02(3H, s), 5.20(2H, s), 6.48-7.92(11H, m) 40 2.22(3H, s),2.88(3H, d), 4.04(3H, s), 5.21(2H, s), 6.70(1H, bs), 7.37(1H, s),7.68(4H, q) 41 2.16(3H, s), 2.85(3H, d), 3.79(3H, s), 4.05(3H, s),5.18(2H, s), 6.91(1H, bs), 6.85-7.62(5H, m) 42 2.04(3H, d), 2.84(3H, d),4.00(3H, s), 5.19(2H, s), 6.75(1H, bs), 6.97-7.56(5H, m) 43 2.20(3H, s),2.90(3H, d), 4.03(3H, s), 5.20(2H, s), 6.60-7.13(2H, m), 7.20-7.60(4H,m) 44 2.17(3H, s), 2.88(3H, d), 4.02(3H, s), 5.20(2H, s), 6.70(1H, bs),6.90-7.70(5H, m) 45 1.98(3H, s), 2.85(3H, d), 4.00(3H, s), 5.20(2H, s),6.41-7.80(6H, m) 46 2.20(3H, s), 2.88(3H, d), 4.02(3H, s), 5.19(2H, s),6.37-8.20(6H, m) 47 2.17(3H, s), 4.03(3H, s), 5.18(2H, s), 6.75(1H, bs),7.23-7.64(5H, m) 48 1.97(3H, s), 2.87(3H, d), 4.01(3H, s), 5.20(2H, s),6.32-7.99(6H, m) 49 2.20(3H, s), 2.87(3H, d), 4.03(3H, s), 5.20(2H, s),6.38-8.09(6H, m) 50 2.18(3H, s), 2.89(3H, d), 4.02(3H, s), 5.18(2H, s),6.49-7.82(6H, m) 51 2.20(3H, s), 2.87(3H, d), 4.03(3H, s), 5.20(2H, s),6.80(1H, bs), 7.40(1H, s), 7.60(2H, d), 7.80(2H, d) 52 2.13(3H, s),2.85(3H, d), 4.00(3H, s), 5.17(2H, s), 6.72(1H, bs), 6.83-7.47(10H, m)53 2.18(3H, s), 2.86(3H, d), 4.04(3H, s), 5.19(2H, s), 6.72(1H, bs),6.95-7.70(10H, m) 54 2.18(3H, s), 2.85(3H, d), 4.00(3H, s), 5.08(2H, s),5.18(2H, s), 6.56-7.31(1H, m) 55 1.98(3H, s), 2.85(3H, d), 4.00(3H, s),5.21(2H, s), 6.68(1H, bs), 7.00-7.39(4H, m) 56 2.01(3H, s), 2.90(3H, d),4.02(3H, s), 5.21(2H, s), 6.71-7.59(5H, m) 57 2.01(3H, d), 2.98(3H, d),4.05(3H, s), 5.19(2H, s)6.70(1H, bs), 6.91-7.39(4H, m) 58 1.95(3H, s),2.85(3H, d), 3.83(3H, s), 5.01(2H, s), 6.62(1H, bs), 6.92-7.55(5H, m) 592.10(3H, s), 2.90(3H, d), 4.03(3H, s), 5.19(2H, s), 6.67(1H, bs),6.95-7.63(4H, m) 60 2.10(3H, s), 2.88(3H, d), 4.05(3H, s), 5.18(2H, s),6.32-7.36(4H, m), 8.01(1H, bs) 61 2.13(3H, s), 2.90(3H, d), 4.01(3H, s),5.19(2H, s), 6.40-7.62(6H, m) 62 2019(3H, s), 2.29(3H, s), 4.01(3H, s),5.18(2H, s), 6.50-7.80(6H, m) 63 2.12(3H, s), 2.83(3H, d), 3.68(6H, s),4.01(3H, s), 5.19(2H, s), 6.62-7.70(6H, m) 65 2.20(3H, s), 2.90(3H, d),4.10(3H, s), 5.20(2H, s), 6.50(1H, t), 6.60-6.90(1H, m), 7.25(1H, s),7.40(4H, q) 66 2.20(3H, s), 2.90(3H, d), 4.05(3H, s), 5.20(2H, s),6.50-6.95(1H, m), 7.21(1H, s), 7.38(1H, s), 7.80(2H, s) 67 2.20(3H, s),2.90(3H, d), 4.05(3H, s), 5.20(2H, s), 5.90(1H, t), 6.60-6.80(1H, m),7.25(1H, s), 7.50(4H, q) 68 2.20(3H, s), 2.50(3H, s), 2.90(3H, d),4.00(3H, s), 5.20(2H, s), 6.60-6.80(1H, m), 7.20(1H, s), 7.40(4H, q) 692.20(3H, s), 2.90(3H, d), 3.00(3H, s), 4.05(3H, s), 5.20(2H, s),6.60-6.80(1H, m), 7.40(1H, s), 7.80-7.90(4H, bs) 70 2.18(3H, s),2.85(3H, d), 4.03(3H, s), 5.18(2H, s), 6.70(1H, bs), 7.35-7.84(5H, m) 712.18(3H, s), 2.30(6H, s), 2.89(3H, d), 4.03(3H, s), 5.18(2H,s)6.53-7.57(6H, m) 72 2.02(3H, s), 2.90(3H, d), 3.59(3H, s), 3.90(3H,s), 5.22(2H, s), 6.73(1H, bs), 6.85-7.36(4H, m) 73 2.00(3H, s), 2.90(3H,d), 4.15(3H, s), 5.21(2H, s), 6.70(1H, bs), 7.18-7.41(4H, m)

TABLE 2-2 δ value (ppm, solvent: CDCl3, internal reference:tetramethylsilane 74 2.16(3H, s), 2.29(3H, s), 2.82(3H, d), 4.00(3H, s),5.18(2H, s), 6.50-7.59(5H, m) 75 2.17(3H, s), 2.35(3H, d), 2.86(2H, d),4.05(3H, s), 5.19(2H, s), 6.70(1H, bs), 6.84-7.51(4H, m) 76 2.10(3H, s),2.90(3H, d), 3.90(3H, s), 4.00(3H, s), 5.20(2H, s), 6.60-6.80(1H, m),7.25(1H, s), 7.20-7.50(3H, m) 77 2.20(3H, s), 2.82(3H, d), 3.90(3H, s),4.00(3H, s), 5.20(2H, s), 6.60-6.80(1H, m), 7.00-7.25(3H, m), 7.30(1H,s) 78 2.10(3H, s), 2.90(3H, d), 3.90(3H, s), 4.00(3H, s), 5.20(2H, s),6.60-7.00(2H, m), 7.25(1H, s), 7.40-7.90(2H, m) 79 1.90(3H, s), 2.80(3H,d), 3.80(3H, s), 4.00(3H, s), 5.20(2H, s), 6.60-7.00(2H, m), 7.18(1H,s), 7.20-7.40(2H, m) 80 2.20(3H, s), 2.88(3H, d), 4.04(3H, s), 5.19(2H,s), 6.66(1H, bs), 7.25-7.55(4H, m) 81 2.00-2.10(3H, m), 2.85(3H, d),4.05(3H, s), 5.20(2H, s), 7.20(1H, s), 7.00-7.50(3H, m) 82 1.90(3H, s),2.85(3H, d), 4.00(3H, s), 5.20(2H, s), 6.60-6.80(1H, m), 7.15(1H, s),6.90-7.40(3H, m) 83 2.20(3H, s), 2.90(3H, d), 4.06(3H, s), 5.20(2H, s),5.25(2H, s), 6.70(1H, bs), 7.00-7.88(4H, m) 84 2.04(3H, s), 2.89(3H, d),4.02(3H, s), 5.20(2H, s), 6.41-7.89(5H, m) 85 2.01(3H, s), 2.90(3H, d),4.01(3H, s), 5.22(2H, s), 6.44-7.98(5H, m) 86 2.23(3H, s), 2.90(3H, d),4.01(3H, s), 5.21(2H, s), 6.37-8.10(5H, m) 87 2.21(3H, s), 2.90(3H, d),4.05(3H, s), 5.20(2H, s), 6.40-8.01(5H, m) 88 2.20(3H, s), 2.88(3H, d),4.00(3H, s), 5.20(2H, s), 6.37-8.23(5H, m) 89 1.83(3H, s), 2.90(3H, d),3.99(3H, s), 5.19(2H, s), 6.41-7.79(5H, m) 90 2.43(3H, s), 3.20(3H, d),4.52(3H, s), 5.75(2H, s), 7.40(1H, bs), 7.82-8.57(4H, m) 91 2.20(3H, s),2.85(3H, d), 3.85(3H, s), 4.08(3H, s), 5.20(2H, s), 6.60(1H, t),7.00(1H, s), 7.22(1H, s)7.28-7.50(2H, m) 92 2.17(3H, s), 2.87(3H, d),4.00(3H, s), 4.05(3H, s), 5.17(2H, s), 6.70(1H, bs), 7.27(1H, s),7.35(1H, s) 93 2.19(3H, s), 2.64(3H, s), 2.81(3H, s), 3.99(3H, s),5.20(2H, s), 6.90-7.65(5H, m) 94 0.82(3H, t), 1.05(3H, t), 2.17(3H, s),3.26(4H, q), 5.20(2H, s), 7.22-7.68(6H, m) 95 1.27(3H, t), 2.90(3H, d),4.05(3H, s), 4.21(2H, q), 6.67(1H, bs), 7.22-8.07(6H, m) 96 2.80(3H, s),2.87-2.84(3H, d), 4.10(3H, s), 5.25(2H, s), 6.64(1H, bs), 7.40-7.95(5H,m), 8.10(1H, s) 97 2.97(3H, d), 3.80(3H, s), 3.83(3H, s), 5.16(2H, s),6.65(1H, s), 7.20-8.00(5H, m) 98 1.19(3H, d), 2.61(2H, q), 4.01(3H, s),5.20(2H, s), 6.76(1H, bs), 7.21-7.68(6H, m) 99 2.90(5H, d), 4.02(3H, s),5.22(2H, s), 6.71(1H, bs), 7.10-7.70(11H, m) 100 2.90(3H, d), 4.00(3H,s), 5.20(2H, s), 6.37-8.04(7H, m) 101 2.82(3H, d), 3.89(3H, s), 5.19(2H,s), 6.71(1H, bs), 7.71-7.81(11H, m) 102 2.24(3H, s), 2.83(3H, d),3.12(1H, bs), 5.26(2H, s), 6.81-7.68(6H, m) 103 2.22(3H, s), 2.91(3H,d), 5.24(2H, s), 5.75(2H, d), 6.70(1H, bs), 7.24-7.90(6H, m) 1042.18(3H, s), 2.90(3H, d), 5.24(2H, s), 5.75(2H, d), 6.70(1H, bs),6.92-7.70(5H, m) 105 2.18(3H, s), 2.83(3H, d), 2.67(2H, m),5.16-5.38(2H, m), 5.19(2H, s), 6.82(1H, bs), 7.26-7.64(6H, m) 1062.18(3H, s), 2.83(3H, d), 5.23(2H, s), 5.25(2H, s), 6.66(1H, bs),7.30-7.62(11H, m) 107 2.17(3H, s), 2.51(1H, t), 2.85(3H, d), 4.78(2H,d), 5.21(2H, s), 6.80(1H, bs), 7.25-7.70(6H, m) 108 2.41(3H, s),2.84(3H, d), 4.05(3H, s), 5.16(2H, s), 6.77(1H, bs), 7.19-7.65(6H, m)109 2.08(3H, s), 2.10(2H, t), 2.89(3H, d), 3.99(3H, s), 4.02(2H, t),7.18-7.96(6H, m) 110 2.20(3H, s), 2.88(3H, d), 4.03(3H, s), 5.20(2H, s),5.60(1H, bs), 7.37(1H, s), 7.47-7.80(4H, m), 8.13(1H, s) 111 3H,s2.20(3H, s), 2.85(3H, d), 3.97(3H, s), 4.03(3H, s), 5.17(2H, s),6.77(1H, bs), 7.35(1H, s), 7.40-7.80(4H, m), 8.05(1H, s) 112 2.20(3H,s), 2.85(9H, m), 4.05(3H, s), 5.20(2H, s), 6.60-6.80(1H, m), 7.20(1H,s), 7.25(1H, s), 7.35-7.95(4H, m) 118 1.62-1.99(4H, m), 2.10(3H, s),3.10(2H, t), 3.37(2H, t), 3.99(3H, s), 5.21(2H, s), 7.22-7.68(6H, m) 1191.18-1.61(5H, m), 2.20(3H, s), 3.00-3.43(4H, m), 3.98(3H, s), 5.21(2H,s), 7.21-7.70(6H, m) 120 2.21(3H, s), 3.18-3.78(4H, m), 3.97(3H, s),5.21(2H, s), 7.22-7.68(6H, m) 121 0.92(3H, d), 1.10(3H, d), 2.20(3H, s),2.00-3.38(6H, m), 3.98(3H, s), 5.05(2H, s), 7.21-7.72(6H, m) 1222.18(3H, s), 2.35-2.55(4H, m), 3.70-3.80(4H, m), 3.94(3H, s), 5.20(2H,s), 7.25-7.67(6H, m) 123 2.18(3H, s), 3.78(3H, s), 4.02(3H, s), 5.09(2H,s), 6.72(1H, bs), 7.22-7.77(6H, m), 8.48(1H, bs) 124 2.27(3H, s),2.58(6H, s), 4.00(3H, s), 5.17(2H, s), 7.21-7.70(7H, m)

TABLE 3-1 Compd. No. Properties 1 m.p. 117-118° C. 11 m.p. 90-92° C. 13Oily matter 14 m.p. 117-119° C. 15 m.p. 81-82° C. 16 m.p. 167-168° C. 17m.p. >200° C. 18 m.p. 139-140° C. 19 Oily matter 20 m.p. 81-82° C. 21m.p. 95-96° C. 22 Oily matter 23 m.p. >200° C. 24 Resinous substance 25Resinous substance 26 Oily matter 27 m.p. 40-41° C. 28 Oily matter 29m.p. 170-171° C. 30 m.p. 93-94° C. 31 Resinous substance 32 Oily matter33 m.p. 85-86° C. 34 m.p. 102-103° C. 35 m.p. 128-129° C. 36 Resinoussubstance 37 m.p. 99-100° C. 38 m.p. 100-101° C. 39 m.p. 124-125° C. 40m.p. 128-129° C. 41 m.p. 99-100° C. 42 m.p. 102-103° C. 43 m.p. 118-119°C. 44 m.p. 84-85° C. 45 m.p. 108-111° C. 46 m.p. 76-78° C. 47 m.p.119-121° C. 48 Oily matter 49 m.p. 94-96° C. 50 m.p. 110-112° C. 51 m.p.133-134° C. 52 Resinous substance 53 Oily matter 54 m.p. 122-123° C. 55m.p. 115-116° C. 56 m.p. 113-114° C. 57 m.p. 133-134° C. 58 m.p.131-132° C. 59 m.p. 77-78° C. 60 m.p. 108-110° C. 61 m.p. 161-162° C. 62m.p. 115-116° C. 63 m.p. 156-157° C. 65 m.p. 140-141° C.

TABLE 3-2 Compd. No. Properties 66 m.p. 91-92° C. 67 m.p. 108-109° C. 68m.p. 136-137° C. 69 m.p. 118-119° C. 70 m.p. 103-104° C. 71 m.p.140-141° C. 72 m.p. 134-135° C. 73 m.p. 139-140° C. 74 m.p. 93-94° C. 75m.p. 86-87° C. 76 m.p. 96-97° C. 77 m.p. 99-100° C. 78 m.p. 117-118° C.79 m.p. 112-113° C. 80 m.p. 135-136° C. 81 m.p. 81-82° C. 82 m.p.115-116° C. 83 m.p. 94-95° C. 84 m.p. 117-119° C. 85 m.p. 101-103° C. 86m.p. 119-121° C. 87 m.p. 108-109° C. 88 m.p. 110-111° C. 89 m.p.140-142° C. 90 m.p. 121-122° C. 91 m.p. 109-110° C. 92 m.p. 117-118° C.93 Oily matter 94 Oily matter 95 m.p. 118-119° C. 96 m.p. 111-112° C. 97m.p. 182-183° C. 98 m.p. 49-50° C. 99 m.p. 112-113° C. 100 m.p. 103-104°C. 101 Resinous substance 102 m.p. 151-152° C. 103 m.p. 98-99° C. 104Resinous substance 105 Resinous substance 106 Oily matter 107 Resinoussubstance 108 m.p. 154-155° C. 109 Oily matter 110 Oily matter 111Resinous substance 112 m.p. 64-65° C. 118 Oily matter 119 Oily matter120 Oily matter 121 Oily matter 122 Oily matter 123 m.p. 166-167° C. 124Oily matter

Formulations Formulation Example 1 Production of Wettable Powder

10 Parts of each compound shown in Table 1 (Compounds Nos. 11 to 124),83 parts of clay, 2 parts of white carbon, 2 parts of ligninsulfonicacid soda and 3 parts of alkylnaphthalenesulfonic acid soda were mixedand pulverized to give wettable powder.

Formulation Example 2 Production of Granules

2.5 Parts of each compound shown in Table 1 (Compounds Nos. 11 to 124),28 parts of bentonite, 52 parts of talc, 2 parts ofdodecylbenzenesulfonic acid soda and 2 parts of lignin sulfonic acidsoda were mixed. To the mixture, 13.5 parts of water was added. Theresulting mixture was kneaded by a kneader, granulated by a granulatorand then subjected to drying and sieving to give granules.

Formulation Example 3 Production of Flowable

5 Parts of each compound shown in Table 1 (Compounds Nos. 11 to 124), 11parts of propylene glycol, 3-parts of SORPOL 7290P (trade name,available from TOHO Chemical Industry Co., Ltd.), 0.1 part of TOXANONEN100 (trade name, available from Sanyo Chemical Industries, Ltd.), 0.2part of ANTIFOAM E-20 (trade name, available from KAO Corporation), 1.5parts of KUNIPIA F (trade name, available from Kunimine Industries Co,Ltd.) and 79.2 parts of water were well mixed. The mixture was wetpulverized to particle sizes of 5 μm or less. A flowable was thusobtained.

Formulation Example 4 Production of Emulsifiable Concentrate

5 Parts of each compound shown in Table 1 (Compounds Nos. 11 to 124) wasdissolved in 50.5 parts of N-methylpyrrolidone. The solution wascombined with 24.5 parts of SAS 296 (trade name, available from NIPPONPETROCHEMICALS COMPANY, LTD) and 20 parts of SORPOL 3880L (trade name,available from TOHO Chemical Industry Co., Ltd.). These were stirred togive a uniform solution. An emulsifiable concentrate was thus obtained.

Test of Herbicidal Effects

Examples of testing the herbicidal activity of the herbicidecompositions of the invention are given below, but it should beconstrued that the invention is in no way limited to those testexamples.

Test Example 1 Upland Field Foliage Treatment

A plastic pot of 130 cm was filled with upland soil. Subsequently, weedseeds of Setaria viridis, Digitaria adscendens, Chenopodium album andStellaria media, and crop seeds of soybean (Glycine max) and wheat(Triticum aestivum), were sowed and covered with soil of about 1 cmthickness. On the 14th day after the sowing, the wettable powderprepared in Formulation Example 1 was diluted with water such that theamount of the active ingredient became 1 kg per hectare, and thenuniformly applied to the plant leaf surfaces. On the 21st day after theapplication, observation and evaluation were carried out according tothe criteria described below.

The results are set forth in Table 4.

Test Example 2 Upland Soil Treatment

A plastic pot of 130 cm² was filled with upland soil. Subsequently, weedseeds of Setaria viridis, Digitaria adscendens, Chenopodium album andStellaria media, and crop seeds of soybean (Glycine max) and wheat(Triticum aestivum), were sowed and covered with soil of about 1 cmthickness. On the next day after the sowing, the wettable powderprepared in Formulation Example 1 was diluted with water such that theamount of the active ingredient became 1 kg per hectare, and thenuniformly applied to the soil surface. On the 21st day after theapplication, observation and evaluation were carried out according tothe aforesaid criteria.

The results are set forth in Table 5.

Test Example 3 Paddy Field Treatment

A plastic pot of 130 cm² was filled with paddy soil, and soil puddlingwas carried out to adjust the submerged depth to 4 cm. Subsequently,seeds of Echinochloa crusgalli, Monochoria vaginalis, Ammanniamultiflora and Scirpus juncoides were sowed, and rice (Oryza sative,variety: Koshihikari) of two-leaf period was transplanted by 2 riceplants of 1 stub per pot at a depth of 3 cm. On the 10th day after thetransplantation, the wettable powder prepared in Formulation Example 1was diluted with water such that the amount of the active ingredientbecame 1 kg per hectare, and then dropped to diffuse on the watersurface. On the 21st day after the dropping, observation and evaluationwere carried out according to the aforesaid criteria.

The results are set forth in Table 6.

<Evaluation Criteria>

Herbicidal activity was evaluated based on the following criteria.

Index: 0-5

-   5: herbicidal effect of not less than 90%, or phytotoxicity of 90%    or more-   4: herbicidal effect of not less than 70% and less than 90%, or    phytotoxicity of 70% or more and less than 90%-   3: herbicidal effect of not less than 50% and less than 70%, or    phytotoxicity of 50% or more and less than 70%-   2: herbicidal effect of not less than 30% and less than 50%, or    phytotoxicity of 30% or more. and less than 50%-   1: herbicidal effect of not less than 10% and less than 30%, or    phytotoxicity of 10% or more and less than 30%

0: herbicidal effect of not less than 0% and less than 10%, orphytotoxicity of 0% or more and less than 10% TABLE 4-1 Herbicidalactivity Compd. No. SV DA CA SM GM TA 11 3 5 5 3 0 0 13 3 4 4 4 0 0 14 55 5 5 0 0 17 5 5 5 5 0 0 18 5 5 5 5 0 0 19 5 5 5 5 0 0 20 2 3 5 5 0 0 215 5 5 5 0 0 23 3 3 4 4 0 0 24 4 3 4 4 0 0 26 4 5 5 5 0 0 27 5 5 5 5 0 028 3 3 4 3 0 0 30 3 4 4 3 0 0 33 4 5 4 4 0 0 34 4 5 4 4 0 0 36 4 5 5 4 00 37 5 5 5 5 0 0 41 5 5 5 5 1 0 42 5 5 5 5 0 0 43 5 5 5 5 0 0 44 5 5 5 50 0 46 5 5 5 5 0 0 47 5 5 5 5 0 0 53 4 5 5 4 0 0 54 4 5 4 4 0 0 56 5 5 55 0 0SV: Setaria viridisDA: Digitaria adscendensCA: Chenopodium albumSM: Stellaria mediaGM: Soybean (Glycine max)TA: Wheat (Triticum aestivum)

TABLE 4-2 Herbicidal activity Compd. No. SV DA CA SM GM TA 57 5 5 5 5 00 59 5 5 5 5 0 0 65 5 5 5 5 0 0 67 4 5 5 4 0 0 70 4 5 5 4 0 0 74 5 5 5 50 0 75 5 5 5 5 0 0 77 3 5 5 3 0 0 81 5 5 5 5 0 0 82 3 5 4 4 0 0 83 3 5 44 0 0 85 4 4 5 5 0 0 86 3 5 4 4 0 0 88 4 5 5 5 0 0 92 5 5 5 5 0 0 94 3 35 5 0 0 98 3 4 4 4 0 0 103 3 4 5 5 0 0 104 3 4 5 5 0 0 105 5 5 5 5 0 0106 3 3 3 3 0 0 111 4 4 5 5 0 0 118 3 4 4 5 0 0 120 4 4 5 4 0 0 122 4 44 4 0 0 124 3 3 4 4 0 0

TABLE 5-1 Herbicidal activity Compd. No. SV DA CA SM GM TA 13 4 4 5 5 00 14 5 5 5 5 1 0 17 4 4 4 4 0 0 18 5 5 5 5 0 0 19 5 5 5 5 0 0 20 3 4 3 40 0 21 4 4 5 5 0 0 23 4 4 5 4 0 0 24 4 3 5 4 0 0 26 4 5 5 5 0 0 27 5 5 55 1 0 28 3 4 4 3 0 0 30 4 3 4 3 0 0 33 4 5 5 5 0 0 34 4 5 5 5 0 0 36 4 45 5 1 0 37 5 5 5 5 0 0 41 5 5 5 5 1 0 43 5 5 5 5 1 0 44 5 5 5 5 0 0 46 55 5 5 1 0 47 5 5 5 5 0 0 51 4 4 4 4 0 0 53 3 5 4 4 0 0 54 3 4 5 5 0 0 555 5 5 5 0 0SV: Setaria viridisDA: Digitaria adscendensCA: Chenopodium albumSM: Stellaria mediaGM: Soybean (Glycine max)TA: Wheat (Triticum aestivum)

TABLE 5-2 Herbicidal activity Compd. No. SV DA CA SM GM TA 56 5 5 5 5 10 57 5 5 5 5 0 0 59 5 5 5 5 0 0 65 5 5 5 5 0 0 67 4 4 5 5 0 0 70 3 3 4 40 0 74 4 5 5 5 1 0 75 4 4 5 5 1 0 77 4 5 5 5 0 0 81 5 5 5 5 1 0 82 4 5 45 0 0 83 5 5 5 5 0 0 86 4 5 5 5 1 0 88 4 4 5 5 0 0 92 5 5 5 5 0 0 94 3 35 4 0 0 98 3 4 4 5 0 0 103 4 5 5 5 0 0 104 4 5 5 5 0 0 105 4 4 4 4 0 0106 3 4 4 4 0 0 111 4 4 5 5 0 0 118 3 3 4 4 0 0 120 3 4 4 4 0 0 122 3 34 4 0 0 124 3 3 5 4 0 0

TABLE 6-1 Herbicidal activity Compd. No. EC SJ MV AM OS 11 5 5 5 5 1 145 5 5 5 1 17 4 4 5 5 0 18 5 5 5 5 0 19 5 5 5 5 0 20 5 4 5 4 0 21 5 5 5 50 23 4 4 5 5 0 24 4 4 5 4 0 26 5 5 5 5 0 27 5 5 5 5 0 30 4 4 5 4 0 31 34 5 4 0 33 5 4 5 5 0 34 5 5 5 5 1 35 5 4 4 4 0 37 5 5 5 5 1 38 5 5 5 5 040 5 5 5 5 0 41 5 5 5 5 0 42 5 5 5 5 0 43 5 5 5 5 1 44 5 5 5 5 1 47 5 55 5 0 49 5 5 5 5 1 53 5 5 5 5 0EC: Echinochloa crusgalliSJ: Scirpus juncoidesMV: Monochoria vaginalisAM: Ammannia multifloraOS: Rice (Oryza sativa)

TABLE 6-2 Herbicidal activity Compd. No. EC SJ MV AM OS 55 5 5 5 5 0 565 5 5 5 0 57 5 5 5 5 0 58 5 5 5 5 1 59 5 5 5 5 0 60 5 5 5 5 0 65 5 5 5 50 67 5 5 5 4 0 73 5 4 5 4 0 76 5 5 5 5 0 77 5 5 5 5 0 81 5 5 5 5 0 86 54 5 5 0 87 5 5 5 5 0 90 5 4 5 5 0 91 5 4 5 5 0 92 5 5 5 5 0 98 5 4 5 4 0103 5 5 5 5 0 105 4 4 5 5 0 111 5 5 5 5 0 118 3 4 4 4 0 119 3 3 4 4 0120 3 3 4 4 0 122 4 3 4 4 0 123 3 3 4 4 0

As shown in Tables 4 to 6, the wettable powder herbicides containing theinventive compound of the formula (1) or (4) exerted excellentherbicidal effects on various upland field weeds or paddy field weeds.They caused substantially no phytotoxicity to wheat (Triticum aestivum),soybean (Glycine max) and rice (Oryza sativa), with herbicidal activityevaluated mostly with the index 0.

Industrial Applicability

The substituted pyrazole compounds of the present invention are novelsubstances synthesized from a pyrazole derivative and ahaloalkyleneoxime ester derivative. They possess excellent herbicidalactivity.

Herbicide compositions containing the substituted pyrazole compounds asactive ingredients have high herbicidal effects and wide herbicidalspectra, can work sufficiently in a small dose, and are harmless tocrops. Therefore, the herbicides containing the compounds as activeingredients are useful in agriculture, horticulture and many otherfields.

1. A substituted pyrazole derivative represented by the formula (1):

wherein: n is 0 or 1; independently a group A is a hydrogen atom, abranched or unbranched alkyl group of 1 to 4 carbon atoms, a branched orunbranched haloalkyl group of 1 to 4 carbon atoms, a cycloalkyl group of3 to 6 carbon atoms, or a phenyl group optionally having substituentgroups; said substituent groups being the same as or different from oneanother and selected from branched or unbranched alkyl groups of 1 to 4carbon atoms, branched or unbranched haloalkyl groups of 1 to 4 carbonatoms, branched or unbranched alkoxy groups of 1 to 4 carbon atoms,hydroxyl group, branched or unbranched haloalkoxy groups of 1 to 4carbon atoms, branched or unbranched alkylcarbonyloxy groups of 1 to 4carbon atoms, cycloalkylcarbonyloxy groups of 3 to 6 carbon atoms,branched or unbranched alkoxycarbonyloxy groups of 1 to 4 carbon atoms,branched or unbranched dialkylaminocarbonyloxy groups of 1 to 4 carbonatoms, branched or unbranched dialkylaminosulfonyloxy groups of 1 to 4carbon atoms, branched or unbranched alkylthio groups of 1 to 4 carbonatoms, branched or unbranched haloalkylthio groups of 1 to 4 carbonatoms, branched or unbranched alkylsulfinyl groups of 1 to 4 carbonatoms, branched or unbranched haloalkylsulfinyl groups of 1 to 4 carbonatoms, branched or unbranched alkylsulfonyl groups of 1 to 4 carbonatoms, branched or unbranched haloalkylsulfonyl groups of 1 to 4 carbonatoms, halogen atoms, cyano group, nitro group, phenyl group optionallyhaving substituent groups (the substituent groups are the same as theabove substituent groups), phenoxy group optionally having substituentgroups on the benzene ring (the substituent groups are the same as theabove substituent groups) and benzyloxy group optionally havingsubstituent groups on the benzene ring (the substituent groups are thesame as the above substituent groups); or said substituent groups beinga group represented by the formula (2):

wherein R₆ and R₇ are the same or different and each denotes a hydrogenatom or a branched or unbranched alkyl group of 1 to 4 carbon atoms; orsaid substituent groups being a group represented by the formula (3):

wherein R₈, R₉ and R₁₀ are the same or different and each denotes ahydrogen atom or a branched or unbranched alkyl group of 1 to 4 carbonatoms; said substituent groups substituting a hydrogen atom at 0 to 5arbitrary positions of the phenyl group; a group D is a hydrogen atom, abranched or unbranched alkyl group of 1 to 4 carbon atoms, a branched orunbranched haloalkyl group of 1 to 4 carbon atoms, an alkenyl group of 2to 4 carbon atoms, an alkynyl group of 2 to 4 carbon atoms, a branchedor unbranched alkoxy group of 1 to 4 carbon atoms, a cycloalkyl group of3 to 6 carbon atoms, a cyano group, a halogen atom, a branched orunbranched alkoxycarbonyl group of 1 to 4 carbon atoms, a branched orunbranched alkylthio group of 1 to 4 carbon atoms, a branched orunbranched alkylsulfinyl group of 1 to 4 carbon atoms, a branched orunbranched alkylsulfonyl group of 1 to 4 carbon atoms, or a phenyl groupoptionally having substituent groups (the substituent groups are thesame as the aforesaid substituent groups), said substituent groupssubstituting a hydrogen atom at 0 to 5 arbitrary positions of the phenylgroup; a group E is a hydrogen atom, a branched or unbranched alkylgroup of 1 to 4 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms,a halogen atom, or a phenyl group optionally having substituent groups(the substituent groups are the same as the aforesaid substituentgroups), said substituent groups substituting a hydrogen atom at 0 to 5arbitrary positions of the phenyl group; groups R₁ and R₂ are the sameor different and each denotes a hydrogen atom, a halogen atom, abranched or unbranched alkyl group of 1 to 4 carbon atoms, or a branchedor unbranched haloalkyl group of 1 to 4 carbon atoms; a group R₃ is ahydrogen atom, a branched or unbranched alkyl group of 1 to 4 carbonatoms, a branched or unbranched haloalkyl group of 1 to 4 carbon atoms,an alkenyl group of 2 to 4 carbon atoms, an alkynyl group of 2 to 4carbon atoms, or a branched or unbranched alkoxyalkyl group of 1 to 4carbon atoms; groups R₄ and R₅ are the same or different and eachdenotes a hydrogen atom, a branched or unbranched alkyl group of 1 to 4carbon atoms, a branched or unbranched haloalkyl group of 1 to 4 carbonatoms, a cycloalkyl group of 3 to 8 carbon atoms which may besubstituted with a branched or unbranched alkyl group of 1 to 4 carbonatoms, an alkenyl group of 2 to 4 carbon atoms, an alkynyl group of 2 to4 carbon atoms, a branched or unbranched alkoxyalkyl group of 1 to 4carbon atoms, a cyanomethyl group, a substituted or unsubstituted aminogroup, or a phenyl group optionally having substituent groups; saidsubstituent groups being the same as or different from one another andselected from branched or unbranched alkyl groups of 1 to 4 carbonatoms, branched or unbranched haloalkyl groups of 1 to 4 carbon atoms,branched or unbranched alkoxy groups of 1 to 4 carbon atoms, branched orunbranched haloalkoxy groups of 1 to
 4. carbon atoms, halogen atoms,cyano group and nitro group, wherein said substituent groups substitutea hydrogen atom at 0 to 5 arbitrary positions of the phenyl group; orgroups R₄ and R₅ are each a benzyl group optionally having substituentgroups on the benzene ring; said substituent groups being the same as ordifferent from one another and selected from branched or unbranchedalkyl groups of 1 to 4 carbon atoms, branched or unbranched haloalkylgroups of 1 to 4 carbon atoms, branched or unbranched alkoxy groups of 1to 4 carbon atoms, branched or unbranched haloalkoxy groups of 1 to 4carbon atoms, halogen atoms, cyano group and nitro group, wherein saidsubstituent groups substitute a hydrogen atom at 0 to 5 arbitrarypositions of the benzene ring; or groups R₄ and R₅ are each an α- orβ-phenethyl group optionally having substituent groups on the benzenering, said substituent groups being selected from branched or unbranchedalkyl groups of 1 to 4 carbon atoms, branched or unbranched haloalkylgroups of 1 to 4 carbon atoms, branched or unbranched alkoxy groups of 1to 4 carbon atoms, branched or unbranched haloalkoxy groups of 1 to 4carbon atoms, halogen atoms, cyano group and nitro group, wherein saidsubstituent groups substitute a hydrogen atom at 0 to 5 arbitrarypositions of the benzene ring; or groups R₄ and R₅ together form afive-membered or six-membered aliphatic ring, wherein said ring may besubstituted with a group selected from branched or unbranched alkylgroups of 1 to 4 carbon atoms, branched or unbranched haloalkyl groupsof 1 to 4 carbon atoms, branched or unbranched alkoxy groups of 1 to 4carbon atoms, branched or unbranched haloalkoxy groups of 1 to 4 carbonatoms, halogen atoms, cyano group and nitro group, and said ring maycontain one or two heteroatoms.
 2. A substituted pyrazole derivativeaccording to claim 1 having the formula (1) in which R₄ is a hydrogenatom and R₅ is a substituted amino group —N(R₁₁,R₁₂) and beingrepresented by the following formula (4):

wherein: n is 0 or 1; each group A, D, E, R₁, R₂ and R₃ denotesindependently the same substituent groups as in the formula (1); andgroups R₁₁ and R₁₂ are the same or different and each denotes a hydrogenatom, a branched or unbranched alkyl group of 1 to 4 carbon atoms, abranched or unbranched haloalkyl group of 1 to 4 carbon atoms, abranched or unbranched alkoxycarbonyl group of 1 to 4 carbon atoms, or aphenyl group optionally having substituent groups, said substituentgroups being the same as or different from one another and selected fromalkyl groups of 1 to 4 carbon atoms, haloalkyl groups of 1 to 4 carbonatoms, alkoxy groups of 1 to 4 carbon atoms, haloalkoxy groups of 1 to 4carbon atoms (these groups may be branched or unbranched), halogenatoms, cyano group and nitro group, wherein said substituent groupssubstitute a hydrogen atom at 0 to 5 arbitrary positions of the phenylgroup.
 3. A process for preparing substituted pyrazole derivatives ofthe formula (1), said process comprising reacting a pyrazole derivativeof the formula (5) with a haloalkyleneoxime ester derivative of theformula (6) to obtain a pyrazole derivative ester of the formula (7):

and hydrolyzing the ester group of the pyrazole derivative ester of theformula (7) in the presence of a base to yield a carboxylic acidderivative of the formula (8) and reacting the carboxylic acidderivative with an amine R₄—NH—R₅ in the presence of a condensationagent:

wherein in the formulae (5) to (8), n is 0 or 1, a group Z is a halogenatom, a group R₁₃ is a methyl or ethyl group, and each group A, D, E,R₁, R₂, R₃, R₄ and R₅ denotes independently the same substituent groupsas in the formula (1).
 4. A process for preparing the haloalkyleneoximeester derivative of the formula (6) as described in claim 3, saidprocess comprising allowing a hydroxylamine derivative of the formula(19) to act on a halopyruvate derivative of the formula (18) in thepresence of a solvent, said hydroxylamine derivative being used in 1 ormore equivalents per equivalent of said halopyruvate derivative:

wherein n is 0 or 1, a group Z is a halogen atom, a group R₁₃ is amethyl or ethyl group, and each group R₁, R₂ and R₃ denotes the samesubstituent groups independently as in the formula (1).
 5. A herbicidecomposition comprising one or more kinds of the substituted pyrazolederivatives of claim 1 as active ingredients.
 6. A herbicide compositioncomprising one or more kinds of the substituted pyrazole derivatives ofclaim 2 as active ingredients.
 7. A substituted pyrazole derivativerepresented by the following formula (1):

wherein: n is 0 or 1; independently a group A is a hydrogen atom, abranched or unbranched alkyl group of 1 to 4 carbon atoms, a branched orunbranched haloalkyl group of 1 to 4 carbon atoms, a cycloalkyl group of3 to 6 carbon atoms, or a phenyl group substituted with 0 to 5substituent groups (0 substituent group means an unsubstituted phenylgroup); said substituent groups being the same as or different from oneanother and selected from alkyl groups of 1 to 4 carbon atoms, haloalkylgroups of 1 to 4 carbon atoms, alkoxy groups of 1 to 4 carbon atoms,haloalkoxy groups of 1 to 4 carbon atoms, alkylcarbonyloxy groups of 1to 4 carbon atoms, alkoxycarbonyloxy groups of 1 to 4 carbon atoms,dialkylaminocarbonyloxy groups of 1 to 4 carbon atoms, alkylthio groupsof 1 to 4 carbon atoms, haloalkylthio groups of 1 to 4 carbon atoms,alkylsulfinyl groups of 1 to 4 carbon atoms, haloalkylsulfinyl groups of1 to 4 carbon atoms (these groups may be linear or branched), halogenatoms, hydroxyl group, cyano group, N-hydroxyimino group, N-methoxyiminogroup, N,N-dimethylaminoimino group, phenyl group, phenoxy group andbenzyloxy group; a group D is a hydrogen atom, a halogen atom, abranched or unbranched alkyl group of 1 to 4 carbon atoms, a branched orunbranched haloalkyl group of 1 to 4 carbon atoms, an alkynyl group of 2to 4 carbon atoms, a branched or unbranched alkoxy group of 1 to 4carbon atoms, an alkoxycarbonyl group of 1 to 4 carbon atoms, analkylsulfinyl group of 1 to 4 carbon atoms or a phenyl group; a group Eis a hydrogen atom, a halogen atom, a branched or unbranched alkyl groupof 1 to 4 carbon atoms or a phenyl group; groups R₁ and R₂ are each ahydrogen atom or a methyl group; a group R₃ is a hydrogen atom, abranched or unbranched alkyl group of 1 to 4 carbon atoms, an alkenylgroup of 2 to 4 carbon atoms, an alkynyl group of 2 to 4 carbon atoms, abranched or unbranched alkoxyalkyl group of 1 to 4 carbon atoms, afluoromethyl group or a benzyl group; groups R₄ and R₅ together form afive-membered or six-membered aliphatic ring which may contain 1 or 2heteroatoms and which may be substituted with an alkyl group of 1 to 4carbon atoms, or independently a group R₄ is a hydrogen atom or abranched or unbranched alkyl group of 1 to 4 carbon atoms, and a groupR₅ is a hydrogen atom, a branched or unbranched alkyl group of 1 to 4carbon atoms, a branched or unbranched haloalkyl group of 1 to 4 carbonatoms, a branched or unbranched cyanoalkyl group of 1 to 4 carbon atoms,a cycloalkyl group of 3 to 6 carbon atoms which may be substituted witha branched or unbranched alkyl group of 1 to 4 carbon atoms, an alkenylgroup of 2 to 4 carbon atoms, an alkynyl group of 2 to 4 carbon atoms, aphenyl group, a benzyl group, or an α- or β-phenethyl group optionallyhaving a (branched or unbranched) alkoxy group of 1 to 4 carbon atoms onthe benzene ring.
 8. A substituted pyrazole derivative according toclaim 7, having the formula (1) in which R₄ is a hydrogen atom and R₅ isa substituted amino group —N(R₁₁, R₁₂), and being represented by thefollowing formula (4):

wherein: n is 0 or 1; each group A, D, E, R₁, R₂ and R₃ denotesindependently the same substituent groups as in the formula (1); andgroups R₁₁ and R₁₂ are the same or different and each denotes a hydrogenatom, an alkyl group of 1 to 4 carbon atoms, a haloalkyl group of 1 to 4carbon atoms or an alkoxycarbonyl group of 1 to 4 carbon atoms (thesegroups may be branched or unbranched).
 9. A herbicide compositioncomprising one or more kinds of the substituted pyrazole derivatives ofclaim 7 as active ingredients.
 10. A herbicide composition comprisingone or more kinds of the substituted pyrazole derivatives of claim 8 asactive ingredients.